IL41578A - Haloalkyl silanes their production and plant growth regulating compositions containing them - Google Patents

Description

41578/2 mix** O'JV'O V' Ki n » ¾ΗΊΛ nio'iiV o»Twain onin q»V Novel haloalkyl silanes, their production and plant growth regulating compositions containing them CIBA-GEIGY A.G.

C. 39739 41578/2 The present invention relates to new agents and processes for the regulation of plant growth by the use of new 0-halogenoethyl-silanes as active substances, also to new -halogenoethyl-silanes and to processes for the production of these silanes. v The new 3-halogenoethyl- silanes of the present invention correspond to formula I CH2 - CH2 - Si - B (I) . wherein A represents a radical -S-R^, -N χ R3 or -CH2-CH2X, represents a radical -CH=CH2'or -CH2CH2 , X represents chlorine or bromine, whereby the radicals R-_, R5 and R? each independently represe C Cl8 al^yl radicals> CrC18 alkyl radicals substituted by alkoxycarbonyl, phenyl, furyl,tetrahydrofuryl or pyridyl radicals, alkenyl and cycloalkyl groups; pheny phenyl radicals 41578/4 mono- or polysubstituted by alkyl- or halogen, monosubs t i uted by C, -C0 alkoxy and benzyl radicals which may be substituted 1 o by halogen; represents alkyl which can be substituted by C^-C^ alkoxy, phenyl, C^-C^ cy.cloalkyl, or by a furyl,tetrahydro uryl enyl which hylthio alkyloxy and halogen; represents hydrogen, or the same as , and alkyl radicals; C -C alkyl radicals substituted by halogen, . cyano, C , -C^ 1 6 l o alkoxy, C2-C8 alkanoyloxy, phenyl, C2-C8 alkoxyalkoxy, C^-C^ alkenyloxy , . C2~Cg alkanoylalkox , pherioxy, ^^ ^12 cyc^oa^ ^-> yl or" a"fury1,- -1- substi¬ cycl'";alkyl , ^ ~^12 c cl°alkenyl; phenyl radicals mono- or polysubstituted b bs tituted by cyano, formyl, alkoxycnrbonyl; benzyl radicals mono- or polysubstituted by halogen, monosubs tituted by alkoxy; the radical R^ can, however, additionally represent the group -CORg wherein Rg stands for alkenyl radical, a C^-Cg halogenoalkyl or C^-C^ halogenoa Ikenyl radical, a ^^'^12 cycloa Iky1 , I • - . a C -CQ alkoxvalkyl, C -C0 alkoxycarbony lalkyl , cyc l°a Ikyla 1 ky1 y a phenoxy or a phenyl radical which can be substituted by halogen, C^-C^ alkyl or C^-C^ alkoxy, and finally, for a - furyl,tetrahydrofuryl or pyridyl iradical; with the proviso, however, that only one of the symbols A and B may represent the respective radical -OR^ or -0R.£ in the case where C represents the methyl group.

By alkyl radicals are meant straight-chain or branched radicals having 1 to 18 carbon atoms, such as, e.g. methyl, ethyl, n- propyl, isopropyl, n-butyl, sec-butyl, n-hexyl, n-octyl, n-dodecyl, n-octadecyl, and so forth. It is particularly the straight-chain and branched alkyl radicals having 1 to 8 carbon atoms vihich form the alkyl moiety of alkoxy, alkylthio or alkoxycarbony1 substituents of an alkyl radical or of a phenyl radical . In the case of halogenoalkyl radicals, these are alkyl radicals having 1 to 6 carbon atoms, which can be substituted by fluorine, chlorine and/or bromine, such as, e.g. trifluoromethyl , 2-chloroethyl, 6-chlorohexyl, etc.. Alkenyl radicals are straight-chain or branched radicals having 3 to 18 carbon atoms, e.g. propenyl, butenyl, octenyl, decenyl or heptadecenyl radicals .

These alkenyl radicals can be mono- or polysubstituted by halogen, such as fluorine, chlorine, bromine and/or iodine. Alkenyl radicals having 3 to 6 carbon atoms, form the alkenyl moiety of alkenyloxy radicals . Alkynyl preferably radicals proforably contain 3 to 8 carbon atoms/ in a straight chain, such as, e.g. 2-propynyl, 2-butynyl or 3-hexyn3'l. By cycloalkyl and cycloalkenyl radicals are meant such radicals having 3 to 12 carbon atoms, such as, e.g. cyclopropyl, cyclopentyl, cyclopentenyl , cyclohexyl or cyclohexenyl , etc.

The β-halogenoethyl-silanes of formula I affect in a varying manner the growth of parts of plants above and below the soil, and have a low toxicity towards warmblooded animals. The active substances cause no morphological changes or damage which would result in the withering of the plant. The compounds are not mutagenic. Their action differs from that of a herbicidal active substance and of a fertiliser. The action corresponds more to the effects which can be observed on application of ethylene to various parts of plants. It is known that the plant itself produces, in various stages of development, ethylene to a varying degree, particularly before and during the ripening process of the fruits, and at the end of the vegetation period with the occurring abscission of fruit and leaves. Since the regulation of ripening and of fruit and leaf abscission by application of chemical substances is of the greatest such as commercial importance in the cultivation of f uit , /citrus fruit, pineapples and cotton, efforts have been directed towards the discovery of compounds with which such effects might be obtained, without the treated plants suffering any kind of damage in the process. Thus, various classes of substances have meanwhile become known with which it has been possible to obtain some of the growth-regulating effects referred to; however, the extent of the range of action of these substances corresponds in no way to that of ethylene. Compounds which under certain conditions release ethylene are known. Such compounds have the disadvantage either in that they are relatively unstable under the influences of weather, because they are very susceptible to hydrolysis, or in that they are phytotoxic. In the South African Patent Specification No. 68/1036, β-halogenoethyl- phos phonic acid derivatives are described as active substances which regulate plant growth. These compounds decompose in and on the plant with the release of ethylene, and are therefore similar in action and range of action to ethylene. By virtue of their very low stability, phosphonic acid derivatives are not able, however, to satisfy the demands made on them. As they are stable only in an acid medium, more precisely in a pH-range below 5, the active-substance concentrates have to be stabilised by the addition of acids . This addition of acid however, limits the range of application of these active substances in view of the resulting phytotoxic effects.

Furthermore, the storage of such sensitive concentrates of active substance presents difficulties.

Further compounds known as herbicidally active substances are halogenoalkyl-xnethyl-silanes cf» US-Patent Specifications Nos. 3,390,976 and 3,390,977, and J.E. Leasure et al. , J.Med. Chem. J3 , 949 (1966)7'. $-Chloroethylmethyl-dimethoxy~ silane was produced by J.K. Leasure et al. (loc.cit) , but has no herbicidal action. The US-Patent Specification No.3,183,076 describes a-chloroethylmethyl-dialkoxy-silanes of the formula CH, R - Si - (OR* )2 wherein R i3 methyl, chloromethy1, ethyl or o-chlorethyl R' is hydrogen, lower alkyl or chloro lower alk l. The activity is given as growth altering in plants e.g. suppression and control of the growth of germinant seeds, emerging seedlings and established plants and for promoting the maturing of crops and facilitate their harvest.

The compounds of the present invention must contain a β-halogeno-ethyl group (not an -chloroethyl ) group, which the plant can split off and use the ethylene thus liberated for its own purpose e.g. weakening of the tissue in the stem which connects a fruit to the branch. (Citrus fruit and olives are the crop wherein use of such compounds is most meaningful because they adhere rather strongly. In citrus fruit it is thus possible to harvest ripe fruit while leaving not ripe fruit and flowers unharmed on the tree by this method.

The compounds of the present invention are structurally different from the known compounds and it has been found that a chloromethyl- or a a-chlorethyl silane does not act in the same manner as the compounds of the present application.

For example, while the compounds of the present invention are very effective in fruit abscission of olives, the known compounds have no effect at all.

The present invention relates to new agents containing as active substances β-halogenoethyl-silanes , which have a stimulating or retarding action on plant growth in the various stages of development of the plants. These agents can contain the usual carrier substances, distributin; agents, and stabilisers protecting against the effects of light and of oxidation. The action of the new agents is to regulate vegetative plant growth and germination power, and to promote the formation of blossoms, the development of fruit and the growth of abscission layers. In the case of monocotyledons, an increase in tillering and branching was observed with a simultaneous reduction of growth in height. There was moreover a strengthening of the support tissues of the stalks in the case of the treated plants. The formation of undesirable side shoots on various types of plants is very greatly reduced; for example, the vegetative growth of grape vines is inhibited. The new compounds also have a secretion- promoting action; for example, the latex discharge in the case of Hevea brasiliensis is promoted, an effect which is of great commercial importance. As tests have shown, the rooting of seedlings and cuttings, as well as the development of tubers in the case of potatoes, is promoted. In addition, there occurs a simultaneous sprouting of dormant rhizomes, a factor which is particularly important concerning the various perennial weeds, such as couchgrass, Johnson grass and cyperus, for these can. then be easily destroyed or suppressed by herbicides. The germination capacity of seeds, such as, e.g. seed potatoes and legumes, is promoted with low concentrations, and inhibited with higher concentrations. Both the one effect and the other can be commercially important. A regulation of the blossoming time and of the number of blossoms is possible in the case of many ornamental and cultivated plants. This effect is a particularly important factor in the growing of pineapples . If all the trees or shrubs blossom at the same time, then the crops can be gathered within a comparatively short space of time. With regard to cucurbitaceae, there occurs a displacement of the blossom sex differentiation in favour of pistillate flowers .

Tests have shown that in the case of fruit trees there occurs a thinning of blossomsand fruit. Furthermore, fruit ripening and fruit colouration are accelerated and improved, e.g. with oranges, melons, apricots, peaches, tomatoes, bananas, bilberries, figs, coffee, pepper, o tobacco and pineapples . As a result of the development of abscission layers, the abscission of fruit and leaves is rendered appreciably more easy. This factor has great commercial significance with regard to mechanical harvesting, e.g. of citrus fruits, such as oranges, grapefruits and olives; or stone fruit such as cherries, damsons, peaches, plums and apricots; or pomaceous ifruit such as apples and pears; or soft fruit such as currants, rasberries and bilberries; or nuts such as walnuts and pecan nuts; or sub-tropical fruits such as coffee, figs and pepper, or cotton. With high concentrations, the defoliation of ornamental plants, such as chrysanthemums, rhododendrons, carnations and roses, is also obtained.

The extent and the nature of the action are dependent on the most diverse factors; they are dependent particularly on the time of application with regard to the stage of development of the plant, and on the application concentration. These factors vary, however, depending on the type of plant and on the effect desired. Thus, for example, lawns are treated during the entire growth period; ornamental plants, of which, e.g. the intensity and number of ,the blossoms are to be increased, before development of the blossom setting; plants of which the fruit is to be sold, or in some other way utilised, immediately after blossoming, or at an appropriate interval of time before the gathering of the crop. Application of the active substances is effected by the use of solid or liquid agents, these being applied to parts of plants above the soil, to the surface of the soil, as well as into the soil itself.

The preferred method is the application to the parts of plants above the soil, for which purpose solutions or aqueous suspensions are most suitable. In addition to solutions and dispersions for the treatment of the growth substrate (soil), dusts, granulates and scattering agents are also suitable.

The essential promotion of the abscission of citrus fruits and bean leaves with the use of agents according to the invention was demonstrated by the following tests.

The active substances are sprayed, in the form of solutions in concentrations of 0.2% and 0.4%, respectively, onto branches, well hung with fruit, of various orange trees. The tests are evaluated after 14 days according to the method developed by W.C. Wilson and C.H. Hendershott [Proc. Am. Soc. Hort . Sc. 90, 123 - 129 (1967)]. The test consists in the measuring of the force in kilograms required to effect the abscission of the f uit. 41578/3 In the case of bean-leaf abscission tests-, segments of bean leaves of the type "Tempo" are immersed in a solution of 0.0027c of active substance; for each active substance, 4-8 segments are left for 6 days in the active substance solution under controlled conditions. On specific days after commencement of the treatment, the number of resulting abscissions (contraction or necking of the stalk in the abscission zone on the leaf-side) is assessed.

Tests with agents containing the following active substances produced excellent results: 2-chloroethyl-bis (benzylthio) -hexyloxy-silane, 2-chloroethyl- (benzylthio) -bis (hexyloxy) -silane , 2-chloroethyl-methyl-benzylthio-benzyloxy-silane , 2-chloroethyl-methyl-bis (benzylamino) -silane , 2-chloroethyl-methyl-bis (octadecylainino) -silane, bis- ( β-bromoethyl) -divinyl-silane , tris- ( β-bromoethyl) -vinyl-silane, tetrakis- ( β-bromoethyl) -silane , 2-chloroethyl-dimethyl-ethoxy-silane, 2-chloroe hyl-dimethyl-octyloxy-silane , 2-bromoe hyl-dimethyl-octyloxy-silane , 2-chloroethyl-dimethyl-benzoxy-silane, 41578/3 -bromoethyl-dimethyl-benzyloxy-silane , -chloroethyl-dimethyl- (propynyl- (2 * ) -oxy) -silane , -chloroethyl-dimethyl- (butenyl- (21 ) -oxy) -silane , -chloroethyl-dimethyl- (4 ' -methoxybenzyloxy) -silane, -chloroethyl-dimethyl-acetoxy-silane , -chloroethyl-dimethyl- (41 -chlorobenzyloxy) -silane , -chloroethyl-dimethyl- ( 2-chloroethoxy) -silane, -chloroethyl-dimethyl- (hexynyl- (3 ' ) -oxy) -silane, -chloroethyl-dimethy.l- (benzylthio) -silane , -chloroethyl-dimethyl- (octylthio) -silane , -chloroethyl-dimethyl- (benzylamino) -silane , -chloroethyl-dimethyl- (octadecylamino) -silane .

Agents according to the invention arc produced in a manner known per se by the intimate mixing and grinding of active substances of the general formula I with suitable carriers, optionally -with the addition of dispersing agents or solvents which are inert to the active substances.

VJater-dispersible concentrates of active substance, i.e. wettable powders, pastes and emulsion concentrates, are active substance concentrates which can be diluted with water to obtain any desired concentration. They consist of active substance, carrier, optionally additives which stabilise the active substance, surface-active substances, and anti-foam agents and, optionally, solvents. The concentration of active substance in these agents is 0.5 - 80%.

The wettable powders and pastes are obtained by the mixing and grinding of the active substances with dispersing agents and pulverulent carriers, in suitable devices, until homogeneity is attained. Suitable carriers are, e.g. the following: kaolin, talcum, bole, loess, chalk, limestone, gT-ou-t - sinter Attapulgite limestone -Vfe-fe-qclay , dolomite, diatomaceous earth, precipitated silicic acid, alkaline-earth metal silicates, sodium and potassium aluminium silicates . (feldspar and mica) calcium and magnesium sulphates, magnesium oxide, ground synthetic materials, fertilisers such as ammonium -sulphate, ammonium phosphate, ammonium nitrate, urea, ground vegetable products such as bran, bark dust, sawdust, ground nutshells, cellulose powder, residues of plant extractions, active charcoal, etc., alone or in admixture with each other, Suitable dispersing agents are, e.g. the following: condensation products of sulphonated naphthalene and sulphonated naphthalene derivatives with formaldehyde, condensation products of naphthalene or of naphthalene-sulphonic acids with phenol and formaldehyde, as well as alkali, ammonium and alkaline-earth metal salts of ligninsulphonic acid, also alkylarylsulphonates , alkali metal salts and alkaline-earth metal salts of dibutylnaphthalenesulphonic acid, fatty alcohol sulphates such as salts of sulphated hexadecanols, heptadecanols , octadecanols , and salts of sulphated fatty alcohol glycol ether, the sodium salt of oleyl methyl tauride, dialkyl-dilaurylammonium chloride and fatty acid alkali metal and alkaline-earth metal salts.

Suitable anti-foam agents are for example silicones.

To these mixtures may also be added additives-stabilising the active substance, and/or non-ionic, anion-active and cation-active substances, which, for example, improve the adhesiveness of the active substances on plants and on parts of plants (adhesives and agglutinants) , and/or ensure a better wettability (wetting agents). Suitable adhesives are, for example, the following: olein/lime mixture, cellulose derivatives (methyl cellulose, carboxymethyl cellulose), hydroxyethylene glycol ethers of mono- and dialkylphenols having 5 - 15 ethylene, oxide radicals per molecule and 8 - 9 carbon atoms in the alkyl radical, ligninsulphonic acid, alkali metal and alkaline-earth metal salts thereof, polyethylene glycol ethers (carbowaxes) , fatty alcohol polyglvcol ethers having 5 - 20 ethylene oxide radicals per molecule av^d 8 to 18 carbon atoms in the fatty alcohol moiety, condensation products of ethylene oxide, propylene oxide, polyvinylpyrrolidones , polyvinyl alcohols, condensation products of urea/formaldehyde, as well as latex products. • The active substances are so mixed, ground, sieved and strained with the above mentioned additives that the solid constituen in the case of wettable powders has a particle size not exceeding 0.02 to 0.04 mm, and in the case of pastes not exceeding 0.03 mm.

Emulsion concentrates and pastes are prepared by application of the dispersing agents such as those mentioned in the preceding paragraphs, organic solvents and water. Suitable solvents are, e.g. the following: ketones, benzene, xylenes, toluene, dimethyljsulphoxide , and mineral oil fractions boiling in the range of 120° to 350°. The solvents must be practically odourless, non- hytotoxic, and inert to the active substances.

Furthermore, the agents according to the invention can be employed in the form of solutions. For this purpose, the active substance (or several active substances) of the general formula I is (or are) dissolved in suitable organic solvents, solvent mixtures, or water. The followin -can be used as organic solvents: aliphatic and aromatic hydrocarbons, chlorinated derivatives thereof, alkylnaphthalenes , or mineral oils on their own or in admixture with each other. The solutions should contain the active substances in a concentration range of from 1 to 20%.

The solid preparations, such as dusts, scattering agents and granulates, contain solid carriers such as those mentioned in the foregoing, and, optionally, additives stabilising the active substance. The particle size of the carriers is for dusts advantageously up to about 0.1 mm; for scattering agents from about 0.075 mm to 0.2 mm; and for granulates 0.2 mm or coarser. The concentrations of active substance in the solid preparations are from 0.5 to 807o.

All the mentioned active substance concentrates may also contain agents stabilising against the effects of light, and antioxidants.

In the following are described several types of preparations containing active substances usable according to the invention.. Where not otherwise stated, the term 'parts' denotes parts by weight .

Grnnnl a e The following substances are used for the preparation of a 57o granulate: parts of 2-chloroethyl- dimethyl- (21 -chloroethoxy) - silane, 0.25 parts of epichlorohydrin, 0.25 parts of cetyl polyglycol ether, 3.50 parts of polyethylene glycol ( "Carbowax" ) , 91 parts of kaolin (particle size 0.2 - 0.8 mm).

The active substance is mixed with epichlorohydrin and the mixture dissolved in o parts of acetone; to the solution are then added polyethylene glycol and cetyl polyglycol ether. The thus obtained solution is sprayed on to kaolin, and the acetone subsequently evaporated in vacuo .

Instead of 5 parts of■ the above active substance, it is also possible to use the following: parts of 2-chloroethyl- (benzylthio) -bis- (hexyloxy) -silane, or parts of bis (2-bromoethyl) -divinyl-silane . .

The following constituents are used for the preparation of a) a 407,, b) a 50%, c) a 25%, and d) a 10% wettable pov^der: a) O pa ts of 2-chloroethyl-- dimethyl- (octyloxy) -silane , pa ts of sodium ligninsulphonate , 1 pa t of sodium dibutyl-naphthalenesulphonate , 54 parts of silicic acid; b) 50 parts of 2-chloroethyl- dimethyl- (dodecyloxy) -silane , parts of alkylaryl sulphonate ("Tinovetin B"), parts of calcium ligninsulphonate, , 1 part of Champagne chalk/hydr oxyethyl cellulose mixture (1 : 1) , parts of silicic acid, 14 pa ts of kaolin; c) 25 parts of 2-chloroethyl- dimethyl- (4 ' -methoxy-benzoxy)- silane, .'5 parts of the sodium salt of oleylmethyl tauride, 2. 5 parts of naphthalenesulphonic acid/formaldehyde condensate, 0. 5 parts of carboxymethyl cellulose, par s of neutral potassium aluminium silicate, 62 parts of kaolin; d) 10 pa ts of 2-chloroethyl- dimethyl- (4 ' -chloroben¾xy) -si: parts of a mixture of the sodium salts of saturated fatty alcohol sulphates, parts of naphthalenesulphonic acid/formaldehyde condensate, 82 parts of kaolin.

The active, substances are intimately mixed, in suitable mixers, with the additives; the mixture is subsequently ground in suitable mills and rollers . Wettable powders are thus obtained which can be diluted with water to give suspensions of any desired conce ration. Such suspensions are employed, e.g. for the removal of undesired side shoots, for the tillering of lavms, and for the rooting of seedlings and cuttings.- etc...

Equally good wettable powders can be obtained if the active substance under a) is replaced by 40 parts of 2-chloro-ethyl-bis (benzylthio) - (hexyloxy) -silane ; or by 40 parts of tris- ( 2-bromoethyl ) -vinyl-silane ; or if the active substance under b) is replaced by 50 parts of 2-chloroethyl-methyl-bis (octadecylamino) -silane , or by bis ( 2-bromoethyl ) -divinyl-silane; or if the active substance under c) is replaced by parts of 2-chloroethyl-methyl-benzylthio-benzyloxy-silane , or by bis (2-bromoethyl) -methyl-vinyl-silane or, finally, if the active subance under d) is replaced by 10 parts of 2-chloroethyl- (benzylthio) -bis (hexyloxy) -silane , or by 10 parts of bis (2-bromoethyl) -dimethyl-silane.

Ernul s ion con con (;r at:e The following cons t tuents are mixed together to produce 2570 emulsion concentrates: a) 25 parts of 2-chloroethyl- dimethyl-benz-bxy -silane, parts of a mixture of nonylpbenolpolyoxyethylene and calcium dodecylbenzenesulphonate, 70 parts of xylene; b) 25 parts of 2-chloroethyl- dimethyl-ethoxy -silane, 10 parts of a mixture of non lphenolpolyoxyethylene and calcium dodecylbenzenesulphonate, 65 parts of cyclohexanone .

This concentrate can be diluted v;ith water to obtain emulsions of any desired concentration. Such emulsions are suitable for the thinning out of blossom and fruit, for the accelerated ripening of fruits, and for the promotion of fruit and leaf abscission.

Equally good emulsion concentrates are obtained if the active substance under a) is replaced by 25 parts of 2-chloroethyl- methyl-benzylthio-benzyloxy -silane, or by tetrakis(2-bromoethyl) -silane; or if the. active substance under b) is replaced by 25 parts of 2-chloroethyl bis (benzyl-thio)- (hexyloxy) -silane, or by 2-bromoethyl-trivinyl-silane .

All β-halogenoethyl-silanes embraced by formula I are new compounds. The new β-halogenoethyl-silanes of formula I wherein A, B and C do not denote hydrocarbon radicals are produced according to the present invention by the reaction of a β-halogenoethyl- trichloro-silane of formula II X - CH2 - CH2 - Si - Cl3 (II) independently with three equivalents -iiree+y chosen from one or more of the following types of mercaptans, amines or alcohols of formulae III, IV, V, VI, VII or VIII: RjSH (III) R5SH (IV) . RySH (V) R2R3 H (VI) R^OH (VII) R OK (VIII) The new β-halogenoethyl-silanes of formula I where A does not stand for a hydrocarbon radical, and methyl is denoted by C alone or by both B and C, are produced in an analogous manner by the reaction of a β-halogenoethyl-methyl-chlorosilane of formula IX ' CI D X - CH2 - CH2 - Si (IX) wherein D is methyl or chlorine, with one or two equivalents of one of the mercaptans, amines or alcohols of the formulae III, IV, V, VI, VII or VIII/ respectively.

In the formulae II and IX of the starting materials X represents chlorine or bromine, and R, , R , R~, R 4' R^, and R-, have the meanings given under formula I.

The β-halogenoethyl-dimethyl-silanes of formula I are produced according to the present invention by the reaction of a β-halogenoethyl-dimethyl-chlorosilane of the formula CH 3 CH 3 with one equivalent of an acid of the formula 0 or of a carboxylic acid anhydride of the formula R - C - 0 - C - Rp o I I i t 8 0 0 to give a compound of the formula CH„ I - CH2 - CH2 - Si - 0 - C - R8 C1I3 and, optionally, the exchange of the radical - 0 - C - R0 I t o 0 for the radical of an alcohol of formula VII R 0H The symbols R^, Rg and X have the earlier defined meanings .

The process is preferably carried out in the presence of solvents and/or diluents which are inert to the reactants . Aprotic solvents are particularly suitable, such as, e.g. aliphatic and aromatic hydrocarbons, e.g. hexane, cyclohexane, benzene, toluene, xylene, halogenated hydrocarbons such as chlorinated ethylene, carbon tetrachloride, chloroform, chlorobeiizene , also ethers and ethereal compounds such as diethyl ether, tetrahydrofuran, etc..

A complete reaction is obtained moreover where the alcohols, mercaptans or amines employed as reactants are used in excess to serve as solvents or diluents.

Furthermore, the addition of an acid-binding agent to the reaction mixture may be necessary in some cases.

Suitable acid-binding agents for this purpose are, in particular, tertiary amines such as trialkylamines , e.g. triethylamine , pyridine and pyridine bases, dialkyl-anilines , etc ..

The reaction temperatures are in the range of 0 to 100°C; the reaction duration can vary from a few minutes to several days, and depends to a great extent on the reactivity of the mercaptans, amines or alcohols employed.

The two starting materials of formula II wherein X represents chlorine or bromine are known. β-Chloroethyl-trichloro-silane can be produced, for example, by reaction f of ethyl-trichloro-silane with chlorine (c^>. L.H. Sommer et al., J.Am. Chem. Soc. 68, 1881 (1946); and β-bromoethyl-trichloro-silane by reaction of ethyl-trichloro-silane with bromine (K.W. Michael, J.Org. Chem. 34, 2832 (1969); or by HBr-addition to vinyl-trichloro- silane according to the method of A.I. Bourne (J. Chem. Soc, Sect. C. 1970, 1740) . Catalysts which can be used for this addition reaction are UV-light, peroxides and radical initiators.

Of the starting materials of formula IX, the chlorine compound wherein X and D represent chlorine is known, and can be produced, for example, by reaction of ethyl- nethyl-dichloro/silane with chlorine (c^. J.K. Leasure et al . , loc . cit .) .

The starting materials of formula IX wherein X represents bromine, and wherein X represents chlorine and D methyl, have not hitherto been described in the literature . β-Bromoethyl-methyl-dichloro-silane is produced by methods known per se by reaction of ethyl-/methyl-dichloro/ silane with bromine, corresponding to the process described by K.W. Michael (loc. cit.) for the production of β-bromo-ethyl-trichloro-silane; or by HBr-addition to vinyl-methyl-dichloro-silane analogously to the mode of reaction describ by A.I. Bourne (loc . cit .) . For these addition reactions the catalyst can be UV-light, peroxides and radical, initiators.

The US-Patent Specification No. 3,183,076 describe a-chloroethyl-methyl-dialkoxy-silanes , which can be used for the promotion of germination and leaf-abscission , etc. β-Chloroethyl-dimethyl-chloro-silane is produced by methods known per se by reaction of ethyl-dimethyl-chloro-silane with chlorine, corresponding to the process described by A.D.Petrov (Doklady Akad.Nauk S.S.S.R. 100, 1107 (1955) for the production of 3-chloroethyl- o diethyl-chloro-silane or by HCl-addition o- vinyl-dimethyl-chloro-silane analogously to a mode of reaction described by G.H.Wagner et al . , (Ind. Eng.Chem., 45 , 367 (1953) .

There is obtained in a similar manner g-bromoethyl dimethyl-chloro-silane by a method known per se (cf.

K.W.Michael, J. Org. Chem. , 34_, 2832 (1969)) by reaction of ethyl-dimethyl-chloro-silane with bromine, or by addition of HBr to vinyl-dimethyl-chloro-silane (cf.

A. I. Bourne, J.Chem.Soc. , Sect . C , 1970 , 1740).

The catalysts for the addition of HCl to vinyl-dimethyl-chloro-silane can be zinc chloride and other Lewis acids. 41578/2 The addition of HBr to vinyl-dimethyl-chloro-silane is catalytically promoted by UV-light, peroxides and radical initiators. β-Halogenoethyl-silanes wherein all the symbols A, B and C are hydrocarbon radicals can be. produced by methods known per se; for example, by reaction of corresponding ethyl-silanes with chlorine or bromine according to the process described by A.D. Petrov et al., [Doklady Akad.Nauk. S.S.S.R. 100, (1955) ]; or by the process described by K.W. Michael, [J.Org.Chem. 34, 2832 (L969) 1 for the production of β-chloroethyldiethyl-chloro- silane or β-bromoethyl-dimethyl-chloro-silane . Preferably, however, these new β-halogenoethyl-silanes are produced by addition of HBr or HC1 to vinyl-silanes , that is, to produce -bromoethyl-silanes of formula lb wherein Y2 represents -CH=CH2 or -CH2-CH2-Br, and X and Z2 each independently represent -CH^, -CH=CH2 or -CH2-CH2-Br, the addition being effected by reaction of hydrogen bromide with the appropriate vinyl-silane derivative of formula lib 41578/2 wherein Y3 represents -CH=CH2 , and X3 and Z3 each independently represent -CH^ or -CH=CH2 , in a molar ratio of at least 1:1; and to produce /3-chloroethyl-silanes of formula Ic Cl-CH2- wherein represents -CH=CH2 or -CH2-CH2-C1, and and each independently represent "CH^, -CH=CH2 or the addition being effected by reaction of hydrogen chloride with the appropriate vinyl-silane derivative of formula lib in molar ration of at least 1:1.

The reaction of a vinylrsilane_of_formula lib..with hydrogen bromide is advantageously performed by irradiation with UV-light and/or in the presence of a catalyst, such as organic peroxides or radical initiators.

Suitable -catalysts are, for example: dibenzoyl peroxide, diacetyl peroxide, di-tert-butyl peroxide, cumene hydroperoxide, dialkoxyazo compounds and azobisisobutyronitrile.

The reaction temperatures can vary, depending on the nature of the final product desired, within wide limits; they are however advantageously between -10°C and +150°C, 'particularly between -10°C and +35°C. Since the reaction is intensely exothermic, it is generally performed with initial cooling of the reaction mixture. It is also possible to carry out the reaction under elevated pressure .

The reaction of a vinyl-silane of formula lib with hydrogen chloride is advantageously performed in the presence of a Lewis acid, and optionally under elevated pressure .

The Lewis acids employed can be the compounds known from the literature: for example, aluminium chloride, ί aluminium bromide, iron(III)fchloride, antimony pentachloride, antimony pentafluoride, tin tetrachloride, zinc chloride and boron trifluoride. The reaction is preferably performed in the presence of aluminium chloride.

In general, it is advisable to carry out the reaction at a pressure of at least 5 bars, and at a temperature of between 0°C and 60°C. It is also possible in certain cases, however, to operate at normal pressure; e.g., for the production of the β-chloroethyltrimethyl-silane known per se (c^. Sommer and Baugham, J .Am.Chem.Soc. 83 , 3346 (1961). wherein the various "Hal" meanings are not identical can be obtained, for example, by reaction of vinyl-silanes of formula lib with a mixture of hydrogen chloride and hydrogen bromide, preferably with UV-light irradiation; or by reaction of -chloroethyl-silanes of formula Ic wherein at least one of the symbols X^, and represents -CHXHH^ with hydrogen bromide in the above described manner.

The vinyl- silanes of formula lib and the hydrogen bromide or hydrogen chloride are used, as defined, in a molar ratio of at least 1:1; preferably, however, the hydrogen bromide or hydrogen chloride is used in a ca . 5 - 60% excess above the stoichiometrically required amount.

The vinyl-silanes of formula lib used as starting products are known; they can be produced, for example, by the action of Grignard compounds on corresponding chlorosilanes .

The following examples serve to further illustrate the process according to the invention. I the attached table there are listed further β-halogenoethyl- silanes of formula I produced by the methods described in the examples .

The temperatures are expressed in degrees Centigrade.

Example 1 (Production of an intermediate) An amount of 59.4 g of 2-chloroethyl- trichloro-silane is dissolved in 750 ml of absolute diethyl ether an addition is then made in the course of one hour at -5° to -10° of a mixture of 34.9 g of he.xan-(l)-ol and 23.7 g of absolute pyridine dissolved in 250 ml of absolute ether. The mixture is afterwards stirred for 12 hours at room temperature; filtration, is then performed and the filtrate concentrated in vacuo. After fractional distillation there is obtained 39.2 g of 2-chloroethyl- hexyloxy-dichloro/-silane ; B.P. : 69 - 72°/0.1 Torr .

Calculated: C 36.5 H 6.5 Si 10.7% Found: C 36.5 H 6.5 Si 11.0% Example 2 (Production of an intermediate) An amount of 59.4 g of 2-chloroethyl-trichloro-silane is dissolved in 750 ml of absolute diethyl ether; an addition is then made in the course of one hour at -5° to -10° of a mixture of 69.7 g of hexan-(l)-ol and 47.5 g of absolute pyridine dissolved in 250 ml of absolute ether. The mixture is subsequently stirred for 12 hours at room temperature; filtration is then performed and the filtrate concentrated in vacuo. After fractional distillation there is obtained 32.5 g of 2-chloroethyl- chloro/-silane ; B.P.: 97 - 102°/0.001 Torr, n?n = 1.4423.

Example 3 (Production of an intermediate) An amount of 35.5 g of 2-chloroethyl-methyl-dichloro-silane is dissolved in 300 ml of absolute diethyl ether; an addition is made in the course of one hour at -5° to -10° of a mixture of 2.6 g of benzyl alcohol and 15.8 g of absolute pyridine dissolved in 100 ml of absolute ether, The mixture is stirred for 12 hours at room temperature; filtration is subsequently performed and the filtrate concentrated in vacuo. There is obtained 53.3 g of 2-chloroethyl- methyl-benzyloxy-chloro -silane ; n!^ = 1.5123.

Example 4 A mixture of 30.3 g of triethylamine and 32.1 g of benzylamine is dissolved in 400 ml of absolute diethyl ether; an addition is made at -5° to -10° in the course of 1 1/2 to 2 hours of 19.8 g of 2-chloroethyl-trichloro-silane dissolved in 100 ml of absolute ether. The mixture is stirred for 24 hours at 0° and for 12 hours at room temperature; filtration is then performed and the filtrate concentrated in vacuo. There is obtained 37 g of tria 2-chloroethyl- j -a(benzylamino) -silane; n?n = 1.5730 U Calculated: Si 6.970 Found: Si 7.1% Example 5 An amount of 13.2 g of 2-chloroethyl- silane is dissolved in 100 ml of absolute diethyl ether; additions are then made at -10°, in the course of 30 minutes, firstly of 12.4 g of benzylinercaptan and then of 7.9 g of absolute pyridine dissolved in 50 ml of absolute ether. The mixture is subsequently stirred for 2 hours at 0° and for 2 hours at room temperature and afterwards refluxed for 36 hours. Filtration is performed; the filtrate is quickly washed with ice cold water, dried, and concentrated in vacuo to obtain 23 g of 2-chloroethyl- "bis (hexyloxy)-di(benzylthio) -silane ; n^Q = 1.5215 Calculated: Si 6.4% Found: Si 6.3% Example 6 (Production of a starting material) 42.3 g of vinyl-methyl-dichlorosilane is cooled to -5° to 0°. Hydrogen bromide is then introduced at this temperature, with UV-irradiation, for a period of 30 to 40 minutes. After completion of the HBr-absorption, the Solution is allowed to stand overnight in a nitrogen atmosphere at room temperature. There is obtained an amount of 61.6 g of the new compound 2-bromoethyl- jmethyl-dichloro/ silane; B.P.: 94° - 96°/57 Torr.

Calculated: Si 12.6% Found: Si 13.0% Example 7 (Production of a starting material) A mixture of 142.3 g of vinyl-methyl-dichlorosilane and 1 g of anhydrous AlCl^ is cooled to -5° to 0° .

Hydrogen chloride is introduced at this temperature, with UV-irradiation, for a period of 90 minutes. After completion of the HCl-abso ption, the product is distilled at 0.1 Torr and at a bath temperature of at most 15° into a flask cooled with dry ice. There is obtained 177.5 g of the known 2-chloroethyl-jfaiethyl-dichloro -silane ; B.P. : 82 - 84°/68 Torr.

Calculated: Si 15.8 Found: Si 16.4 Example 8 (Production of a starting material) A 300 ml steel autoclave fitted with magnetic stirrer, thermocouple element and cooling device is charged with 60 g (0.5 mole) of vinyl-dimethyl-chlorosilarte and 0.3 g of anhydrous zinc chloride. The apparatus is flushed twice with nitrogen, and hydrogen chloride then injected portionwise, with stirring, until an internal pressure of 34 bars is obtained. The temperature is raised to 40° and maintained by repeated cooling at 40 - 50° for one hour, during which time the consumed amount of hydrogen chloride is continuously replenished to maintain a constant pressure of 34 bars.

After cooling, the reaction product is distilled over at room temperature and 0.1 Torr, to effect the removal of the ZnC^-catalyst , into a cooling trap cooled to -70°; and subsequently fractionated at 60 Torr through a 10 cm Vigreux-column to obtain 7.1 g of 2-chloroethyl-(,/dimethyl-chloro -silanej B.P.: 70 - 72°/60 Torr.

Example 9 (Production of a starting material) An amount of 725 g of vinyl-dimethyl- chlorosilane is cooled to -5° to 0°; hydrogen bromide is then fed in at this temperature, with UV-irradiation, for 45 to 60 minutes. After completion of the HBr-abso ption, the unreacted hydrogen bromide is expelled with nitrogen, and the solution fractionated through a 20 cm Vigreux-column .

There is obtained 1080 g of 2-bromoethyl- ^dimethyl-chloro^-silane; B.P.: 65 - 66° /13 Torr .

Calculated : Found : Si 13.39 13.56 Example 10 An amount of 60.4 g of 2-bromoethyl-^dimethyl-chloro^-silane is dissolved in 36 g of acetic acid anhydride, and the solution allowed to stand in a closed vessel for 48 hours at room temperature. The solution is fractionated through a 10 cm Vigreux column.

There is obtained 19.6 g of 2-bromoethyl- /dimethyl-acetyloxy -silane; B.P.: 43° - 44°/0.6 Torr .

Calculated ; Found : Si 12.5 12.4 Example 11 An amount of 30.2 g of 2-bromoethyl~dimethyl-chloro-silane is dissolved in 350 ml of absolute diethyl ether; an addition is then made at -5° to -10° within 5 to 10 minutes of 6.9 g of ethyl alcohol and 11.9 g of absolute pyridine, both constituents dissolved together in 100 ml of absolute ether. Stirring is carried out for a further hour at 0°, and refluxing then performed for 18 hours.

The reaction mixture is filtered, and the filtrate concentrated in vacuo to obtain 13.1 g of 2-bromoethyl- B.P.: 67 - 69°/14 Torr.

Calculated : Found : Si 14.6 14.1 Example 12 A mixture of 10.1 g of triethylamiiie and 10.7 g of benzylamine is dissolved in 150 ml of absolute diethyl ether; an addition is then made at -5° to -10° within one hour of 15.7 g of 2-chloroethyl-dimethyl-chlorosilane dissolved in 50 ml of absolute ether. The mixture, is stirred for 24 hours at 0° and for 12 hours at room temperature. It is then filtered and the filtrate concentrated in vacuo.

There is obtained 16.8 g of 2-chloroethyl- ^dimethyl-(benzylamino) -silane .

Example 13 An amount of 15.7 g of 2-chloroethyl-dimethyl-chloro- silane is dissolved in 200 ml of absolute diethyl ether; additions are ; then made at -10° within 30 minutes firstly of 12.4 g of benzylmercaptan, and then of absolute pyridine dissolved in 50 ml of absolute ether. The mixture is stirred for 2 hours at 0° and for 2 hours at room temperature, and then refluxed for 18 hours. It is subsequently filtered and the filtrate concentrated in vacuo .

There is obtained 19.8 g of 2-chloroethyl-^dimethyl- (benzylthio) -silane .

Example 14 CH--CH, 2 or Br-CH2-CH2-Si-CH2-CH2-Br .kw. Br-CH2 -CH2 ·- Si -CH2 - CH2 ■ CH-CIL CH=CH, A vigorous flow of dry hydrogen bromide is fed at a temperature of -5°, with UV-irradiation, into 17.5 g (0.13 mole) of tetravinyl-silane . After commencement of the exothermic reaction, hydrogen bromide is further introduced with cooling (-5 to 0°) until the absorption of hydrogen bromide is ca . 25 g. The reaction mixture is subsequently fractionated under 0.001 Torr through a Vigreux column to obtain 15.3 g (40% of theory) of bis- (β-bromoethyl) -divinyl-silane and 13.4 g (27% of theory) of tris- (β-bromoethyl) -vinyl-silane .

Analyses : bis- (β-bromoethy1) -divinyl-silane; B.P.Q QQ-^ = 78° Calculated: C 32.2% H 4.7% Si 9.4% Br 53.7% Found: C 32.4% H 4.7% Si 9.8% Br 53.4% tris- (ft-bromoethyl) -vinyl-silane; B-P-Q Q1 = ^6° Calculated: C 25.3% H 4.0% Si 7.4% Br 63.3% Found: C 25.6% H 3.9% Si 7.8% Br 62.4% Example 15 Br-CII2 -CH2- Si-CH2 -CHΊ -Br CH2-CIl2-Br Dry hydrogen bromide is introduced, with UV-irradiation, into 20.4 g (0.15 mole) of tetravinyl-silane, with the temperature being raised from 0° to 140°. After 5-6 hours the hydrogen bromide absorption has attained a level of 93%; the reaction mixture is cooled, whereupon tetrakis-(β-bromoethyl) -silane crystallises out. After recrystallisation from carbon tetrachloride with the addition of active charcoal, there is obtained 45 g (65% of theory) of tetrakis- (jB-bromoethyl) -silane, M'.P. 90 - 91°.

Analysis : Calculated: C 20.9% H 3.5% Si 6.1% Br 69.5% Found: C 20.9% H 3.5% Si 6.0% Br 69.8% Example 16 Br-ClJ 29 --cuill2-- CH2-CH2-Br CH3 Dry hydrogen bromide is introduced, with UV-irradiation at -5° to 0° into 17.0 g (0.151 mole) of dimethyl-divinyl-silane; the reaction occurring is intensely exothermic, and the hydrogen bromide absorption after 30 minutes is already 99%. The reaction product is fractionated at 10 Tor through a Vigreux column to obtain 31.4 g (7670 of theory) of bis- (β-bromoethyl) -dimethyl-silane; B.P.-^ = 117°.

Analysis : Calculated: C 26.3% H 5.1% Si 10.2% Br 58.4% Found: C 26.5% H 5.1% Si 10.4% Br 58.0% Example 17 Br ~C11 B -CH At a temperature of -5° to 0° and with exposure to UV-radiation, hydrogen bromide is fed into 54.4 g (0.4 mole) of tetravinyl-silane ; the supply of hydrogen bromide is continued for ca. 90 minutes, with continuous cooling and stirring of the reaction mixture, until ca . 68 g of hydrogen bromide has been absorbed. The following β-bromoethyl-silanes are obtained after f actionating of the reaction mixture through a 10 cm Vigreux. column: β-bromoethyl-trivinyl-silane, B.P.Q OO5 = 38-40° yield: 3 g (3.5% of theory); bis- ( -bromoethyl) -divinyl-silane, B.P.Q QQ^ ~ 76-78°, yield: 37.2 g (31.5% of theory); theory).

It is possible to obtain from7 the distillation residue, by recrystallisation from cyclohexane or from n-hexane, a further 4 g (2.2% of theory) of tetrakis- (β-bromoethyl) -silane; M.P. 91.

A separation of the β-bromoethyl-silanes obtained is in most cases not necessary for their use in agents according to the invention.

Example 18 At a temperature of -10° to +35° and with exposure to UV-radiation, hydrogen bromide is fed for 4 hours into 50 (0.4 mole) of methyl-trivinyl-silane , until an increase in weight of 79 g is recorded. The reaction mixture is fractionated through a 10 cm Vigreux-column to obtain the following β-bromoethyl-silanes : β-bromoethyl-methyl-divinyl-silane, B.P.„ „- _ 34-37°, yield: 3.3 g (4% of theory); bis- (β-bromoethyl) -methyl- inyl-silane , B . P . = 79-80°, 0.01 yield: 49.7 g (44% of theory) tris- (β-bromoethyD-methyl-silane, B.P.n n!- = 134-135°, yield: 47.7 g (33% of theory) If the tris- (β-bromoethyl) -methyl-silane is recrystallised from n-hexane, then a white crystalline product, M.P. 64°, is obtained.

A separation of the β-bromoethyl-silanes obtained is in most cases not necessary for their use in agents according to the invention.

Example 19 Cl-CH2-CH2- 2-C1 or CI] ., Cl-CH2 -CH2-Si-CH2 -CH2 -C l CH 2 - CH ? -C 1 Ari amount of 62.1 g (0.5 mole) of methyl-trivinyl-silane is placed into a 300 ml steel autoclave fitted with magnetic stirrer, thermocouple element and cooling device and containing a nitrogen atmosphere. At a temperature of -5 to 0°, hydrogen chloride is injected portionwise until an internal pressure of 30 bars is obtained, The reaction mixture is subsequently stirred for 2 1/2 hours at 0 to 20°, while the amount of hydrogen chloride is continuously replenished to maintain a constant pressure of 30 bars . A total amount of 90 g of hydrogen chloride is injected. Fractionating of the reaction mixture through a 10 cm Vigreux column yields the following β-chloroethyl-silanes: β-chloroethyl-methyl-divinyl-silane, = 62-65°, yield: 19 g (23.7% of theory); bis- (/3-chloroethyl) -methyl-vinyl-silane, B.P.Q Q-^ = 64-67°, yield: 20.7 g (21% of theory); tris- (jS-chloroethyl)-methyl-silane, B.P.Q 0QL = 98-103°, yield: 4.0 g (3.5% of 'theory) .

Compounds of formula I CH - CH„ - X I B B R^S R?S R5S R2R3 R2R3N R2R3N R.O 6 CH, Table 1 Table 2 Table 3 41578/2 Table 4 A = R- -S B - R.O C X o Physical data ^ is: R6 is: Ethyl Ethyl CH3 CI II Bu yl CI II Octyl CI II Dodecyl CI Octadecy1 CI Butyl 6- Chlorohexyl CI II 2- Butyloxyethyl CI 2-Ethylthioethyl CI II Benzyl CI n20 = 1.4466 II 2- Allyloxyethyl Br Octyl 2- Phenoxyethyl CI II 2-Buteny1 CI II 2- Propynyl CI 3-Hexynyl Br Benzyl Cyclohexylme thy1 CI 11 Cyclohexyl CI II 3-Phenyl-2-propenyl CI II Benzyl CI 1.5353 Phenyl Br Butyl 3- Chiorophenyl CI 4-Chlorobenzyl Octyl CI - romophenyl 4-Bromophenyl CI Cyclohexyl Cyclohexyl It Br 4-liethoxypheny1 3·, 4-DimethyIphenyl II CI 3-Methylphenyl Octyl CI 2-Propenyl Octyl CI ' Table 5 41578/4 Compounds of formula I CH.

X - CH _ C1L Si - A I CH, Table 7; Λ = O-R^ X Physical data 130 Ethyl CI 131 Ethyl Br' B.P. 67 - 69° /U Torr 132 n-Butyl CI 133 Isobutyl CI 134 sec. Butyl CI 135 Isopropyl CI 136 Hexyl Br B.P. 131° /O , Torr 137 2-MethyIbutyl CI 138 3-Methylbutyl ' CI 139 1,3-DimethyIbutyl CI 140 Octyl CI 141 1-Methylheptyl CI 142 Decyl Br 143 Undecyl CI 144 Dodecyl CI 145 Hexadecyl CI 146 Octadecyl CI 147 2-Chloroethyl CI 6-Chlorohexyl CI 6-Chlorohexyl Br 2 -Methoxyethyl CI 2-Ethoxyethyl CI 2-Isopropyloxyeth l CI 2-Propyloxyethyl CI 2-Butyloxyethyl . CI 2-lIexyloxyethyl Br 2- (2-Ethoxyethoxy) ethyl CI 2- (2-Me thoxyethoxy) ethy1 CI 2- (2-Butyloxyethoxy) ethyl Br 2-Allyloxyethyl CI 2-Aethylthioethyl CI 2-Octylthioethyl CI 3-Phenylpropyl Br 2-Phenylethyl CI •2-Phenoxyethyl CI 2-Propenyl CI 2-Bu enyl CI 2-Butenyl Br B.P. 80 - 82°/0.15 3 , 7-Dimethyl-2-octenyl CI -Undecenyl CI 9-Octadecenyl CI 3 , 7-Dimethyl-7-octenyl CI . 3 , 7-Diwethyl-2 , 6-octadienyl ;Br nD - 1 4748 2-Propynyl CI 2-Propynyl Br l-P):opyl-2 -propinyl CI 3-Hexynyl CI Physical data 177 3- Chloro-2-butenyl CI 178 3-Phenyl-2-propcnyl CI 179 3 -Phany1- 2 -prope.ny1 Br n = 1. 5A 90 180 2- (l-Methylethenyl)ethyl C 181 2- Cyanoethyl CI 182 Ethoxycarbonylmetliyl CI 183 1-Ethoxycarbonylethyl) - Br 184 Butoxycarbony1 IV!ethy1 CI 185 Cyclohexyl CI 186 Cyclohexylmethyl CI 187 3-Cyclobex lpropyl Br "189 Benzyl CI B.P. 90 - 95°/0.3 190 Benzyl Br. B.P. 85 - 87°/0.08 191 A - Chlorobenzyl CI 192 A - Chlorobenzyl Br 193 A -Me hoxybenzyl CI 194 2 , -Dichlorbenzyl CI 195 A-Methylbenzyl CI 196 Phenyl CI 197 A-Chlorophenyl CI 198 3-Chlorophenyl CI 199 3, A-Dichlorophenyl CI 200 3 ,5-Dichlorophenyl CI 201 A-Bromophenyl CI 202 -Me hoxypheny1 CI 203 A-Me hoxyphenyl Br n^ = 1..A708 41578/2 41578/3 Table 8 Λ - 0-R,; V, ■■= -CO- X Physical data i 217 Methyl CI 218 Methyl Br A3 - AA°/0.6 Torr 219 Ethyl Cl 220 Ethyl Br 221 Isopropyl CI 222 l-But 1 propyl CI. 223 Pen yl' CI 224 Octyl CI 225 Heptyl CI 226 llndecyl CI 227 Pentadecyl CI 228 Heptadecyl CI 229 2-Propenyl CI 230 2-Propenyl Br 231 1-P open l CI 232 9-Decenyl CI 233 1 , 3~Pentadienyl CI 234 8 j 11-Heptadecadie.nyl CI 235 2-Chloroethyl CI 236 2-Bromoeth}7l CI 237 l-Bromopentyl CI 238 10-Bromodecyl CI 239 10-Bromodecyl Br 240 cis -2-Chloroethenyl CI 241 cis- 2-Chloroethenyl Br 242 Phenylmethy1 CI 243 2-Phenyl ethyl CI 244 k -Ch lorophenylmethyl CI 245 3-Me hyl henyl CI - ' - 41578/3 41578/2 A = -N /R2 Table 9 N R.

Physical data R i R3 κ j 270 j Ethyl ! Ethyl CI 271 ! H ! Butyl CI 1 272 j H 1 Butyl Br 273 ' Octyl 1 H CI 274 j H Dodecyl CI 275 j H Dodecyl Br 276 j H Octadecyl CI ί 277 j H 2-Propenyl CI 278 j H 9-Octadccenyl Br 1.4664 1 279 ; H 2-Propynyl CI 280 i H 1 , 2 , 2 , -Trimethylpropyl CI 281 H l-Methylhexyl CI 282 H Pentyl CI 283 H Decyl CI 284 H 2-.ethylhexyl CI 285 H Hexa decyl CI 286 H Cyclohexyl CI 287 H Cyclohexylmethyl CI 288 H 2-Methoxyethyl CI 2 89 H 3-1 sopropy1oxypropy1 ci 290 H . 2,2-Diphenylethyl CI 291 H Benzyl CI 292 H Benzyl Br 293 H -Chlorobenzyl CI 294 H 3-Chlorobenzyl CI 295 H 3 } 4 -Dichlorobenzyl CI 296 H 4-Methoxybenzyl CI 297 H Phenyl CI 298 H - Bromopheny 1 CI 299 11 -Methoxypheny1 CI 300 4-Me hylthiophenyl Br 1.5826 H 301 H 3-Me hylphenyl CI 302 Meth l Benz l CI 41578/2' Table 10 A - s -R X Physical data 307 Ethyl CI 308 Butyl CI 309 Octyl CI 310 Octyl Br 311 Dodecyl CI 312 Octadecyl CI 313 Methox carbonylethyl CI 314 3-Phen 1propy1 CI 315 Cyclohexyl CI 316 2-Propenyl CI 317 Phe yl CI 318 Phenyl Br 319 4-Bromophenyl CI 320 A-Chlorophenyl ci 321 A-te t . Butylphenyl CI 322 A-Bromo-3-methylphenyl CI 323 A-MeLhoxyphenyl CI 324 A -Methoxypheny1 Br 325 3-Me hylphenyl CI 326 Benzyl CI 327 Benzyl Br 328 A-Chlorobenzyl CI 329 -Chlorobenzyl Br 330 3 , A-Dimethylpheny1 CI 1

Claims (5)

1. L.) Composition for the regulation of plant -growth for the purpose of increasing and facilitating the production of useful parts of plants, containing as active substance at least one /S-halogenoethyl-silane of formula I A X - CH2 - CH2 - Si - B j (I) wherein A represents a radical -S-R1} or -CH -CH R2 B represents a radical -SR,-, -N*^ , -OR^, -CH^ R. ■CH=CH2or -CH2CH2X, C represents a radical -SR.,, -N^ , -CH=CH2 -CH3 or -CH2-CH2X, and R3 X represents chlorine or bromine, whereby the radicals R^, R^ and R^ each independen ly represent alkyl radicals substituted by alkoxycarbonyl , phenyl, furyl,tetrahydrofuryl or pyridyl radicals, cycloalkyl groups; phenyl » phenyl radicals 41578/3 mono- or polysubstituted by alkyl or halogen, monosubstituted | by C, -C0 alkoxy and benzyl radicals which may be substituted J 1 o by halogen; R^ represents- c^_c13 alkyl which can be substituted alky rad ca s substituted by halogen, cyano, alkoxy, C2~cQ alkanoyloxy, phenyl, C2-C8 alkoxyalkoxy , C^-C^ alkenyloxy, > alkylthio and'C2~Cg alkoxycarbonyl orafuryl,, tetrahyo^furyl or pyridyl radical- C„-C, Q alkenyl , C-,-C-0 alkenyl substi- ' J Io J 1o tuted b/ phenyl, C^-C^ halogenoalkenyl , C3-Cg alkynyl, C ~C12 cycloalkyl, alkenyl; phenyl radicals mono- or polysubstitu alkyl or halogen, phenyl monosubstituted by cyano, fo alkoxy, C2~Cg alkanoyl and C2~Cg alkoxycarbonyl; benzyl radicals mono- or polysubs ituted by halogen, monosubstituted by alkoxy; the radical R^ can, however, additionally represent the group -CORg wherein Rg stands for C]^~c^ alkyl or C2~ciQ alkenyl radical, a cycloalkyl, : . a (-'2~^8 a ^ ^oxya Iky1 , ^2_<½ a lkoxycarbony la Iky1 , Iky1 a phenoxy or a phenyl radical which can be substituted by halogen, C^-C^ alkyl or C^-C^ alkoxy, and finally, for a - furyl,terahydrofuryl or pyridyl .radical; with the proviso, however , that only one of the symbols A and B may represent the respective radical -OR^ or -ORg in the case where C represents the methyl group.
2. 2. )conposition according to Claim 1, containing as active substance a β-halogenoethyl-silane of formula I wherein A represents a radical B represents a radical anc* C represents a radical -SR-,, > °': methyl group, 3 wherein the radicals to R^ are defined as in Claim 1, except that R4 does not represent the group -CORy> and only one of the symbols A and B may represent the respective radical. -OR, or -OR-' in the case here C represents the methyl group.
3. 3. )composition according to Claim 1, containing as active substance a β-halogenoethyl-dimethyl-silane of the formula A I X - CH, CH, Si CH. CH. wherein X represents chlorine or bromine, and R2 A represents a radical -OR^, , or -SR-^, 41578/2 wherein to are defined as in Claim 1, with inclusion of the meaning "CORg for R^ .
4. 4. ) Composition according to Claim 1, containing as active substance a /3-halogenoethyl-silane of formula I wherein B and C each independently represent "CH^, -CH=CH2 or -CH2-CH-X, and A represents -CH=CH2 or -CH2-CH2-X.
5. 5. ) Process for the regulation of plant growth, wherein plants and parts of plants, or the growth substrate of plants, are treated with β-halogenoethyl-silanes of formula I of Claim 1. 6.) A method for the acceleration of the ripening of fruit and facilitation of their abscission as well as for the promotion of the resinous exudation in trees, particularly of the latex flow in rubber trees (Hevea) which consists in spraying fruit bearing or resin producing trees with an effective amount of a compound of formula I, of Claim 1 or a composition contaiing it. 7.) New β-halogenoethyl-silanes of formula I A X - CH2 - CH2 - Si - B (I) C wherein X, A, B and C have the same meanings as in formula I of- Claim 1. 41578/3 8.) Process for the production of β-halogenoethyl· silanes of formula Ϊ2 CH2 - CH2 - St - ½ (lb) Z2 wherein * Y2 represents -CH=CH2 or -CK2-CH2-X, and X2 and Z2 each independently represent -CH^ -CII-CH7 or -CH2-CH2-X, which comprises reacting hydrogen chloride or hydrogen bromide with the appropriate vinyl-silane derivative of the formula CH9 « CH - Si - X3 . (IIb) wherein represents -CH=CH2? and X and each independently represent -Cll or -CD^CIU, in a molar ratio of at least 1:1. 9.) Process according to Claim 8, wherein the reaction is performed by irradiation with UV-light, and/or in the presence of a catalyst I \ r 10.) Process according to Claim 9, wherein the employed catalyst is a Lewis acid, particularly aluminium chloride.