AU463569B2 - Agent forthe regulation of plant growth - Google Patents

Description

34. 26 7 71

The present invention relates to new agents and pr<

for the regulation of plant growth by the use of j3-halogen-el silanes as active substances, also to new P-halogen-ethyl-si.

and to processes for the production of these silanes.

The -halogen-ethyl-silanes contained as active sul

stances in the new agents correspond to formula I: 0 R1

X CH 2 CH 2 Si 0 2 (I)

Y

The symbols in this formula have the following meanings: X represents chlorine or bromine, Y represents chlorine or t

radical -OR 3 R1 R 2 and R 3 represent, independently of each

other, alkyl radical, alkyl radicals substituted by halogen,

alkoxy, alkenyloxy, alkylcarbonyl, halophenoxy, phenoxy, cyc

alkylthio, alkoxy-carbonyl, by a heterocyclic radical and/ox

and trialkyl-ammonio, alkenyl or halogenalkenyl, alkynyl, cy

alkyl, phenyl radicals optionally mono- or polysubstituted t

cyano, nitro, alkyl, halogenalkyl, alkoxy, alkylthio, formy]

phenoxy, alkanoyl and/or alkoxycarbonyl, benzyl radicals opt ly mono- or polysubstituted by alkyl, alkoxy and/or halogen;

or more of the symbols R1 R2 and R3 can also represent the

-CO-R 4 wherein R4 stands for an alkyl, alkenyl or alkynyl ri

a halogenalkyl or halogenalkenyl radical, a cycloalkyl or c:

alkenyl radical, an alkyl or alkenyl radical substituted by

alkyl or phenyl, whereby phenyl can be substituted by alkyl

alkoxy and/or halogen, an alkoxy-alkyl, an alkoxycarbonylal:

a benzoylalkyl radical, a phenyl

463.5

34,2 67 p radical optionally substituted by halogen, lewer)alkyl or /ewer

alkoxy, or a heterocyclic 5- or 6-membered radical, R and R2,

also with the signification of -CO-R together with the

adjacent atoms, can also form a silicium containing saturated

or unsaturated heterocyclic ring system.

By alkyl radicals in formula I 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, etc.. Especi-

ally the straight-chain and branched alkyl radicals having 1 to

8 carbon atoms form the alkyl substituents or the alkyl moiety

of alkoxy, alkylthio, di- and trialkylammonio or alkoxycar-

bonyl substituents of an alkyl radical or of a phenyl radical.

Halogenalkyl radicals 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-chloro-

hexyl, etc.. By alkenyl radicals are meant, in formula I,

straight-chain or branched radicals having 3 to 18 carbon atoms,

e.g. propenyl, butenyl, octenyl, decenyl, heptadecenyl radi-

cals. These alkenyl radicals can be mono- or polysubstituted

by halogens, such as fluorine, chlorine, bromine and/or iodine.

Alkenyl radicals having 3 to 6 carbon atoms form the alkenyl moiety of alkenyloxy radicals. Alkynyl radicals preferably con-

tain 3 to 8 carbon atoms in a straight chain, such as, e.g.

2-propynyl, 2-butynyl or 3-hexynyl. By cycloaliphatic radicals are meant mono- or polycyclic cycloalkyl or cycloalkenyl radi-

cals having 3 to 12 carbon atoms, such as, e.g. cyclopropyl,

cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, bicyclo-

3- 463.569

34,267 /71

heptyl, etc. or 6-Membered heterocyclic radicals as R4 or as substi

tuents of alkyl radicals RI R2' R 3 may be saturated or unsatu ox and contain 1 or 2 hetero atoms, especially nitrogen and/or

or sulfur. Hetero-cyclic ring systems containing the Si-atom

being formed by radicals R1 and R2 including also the type -C

may be saturated or unsaturated, the bridging hydrocarbon moie

of R1 R2 being an alkylene or alkenylene member. Anions of

or -trialkylammonio radicals (which may be considered as salt-

of a dialkyl amino radical) are e.g. those of hydrogen halides

hydrohalogenic acids, alkyl sulphonic acids, alkyl phosphoric

acids etc.

The B-halogen-ethyl-silanes of formula I affect in a vary below manner the growth of parts of plants situated above and ir ground; they are not phytotoxic in the usual concentrations which they are applied, and have a low toxicity.towards warm-

blooded animals. The active substances produce no morphologic

changes or damage which would result in a withering of the pli

The compounds are not mutagenic. Their action differs from tl

of a herbicidal active substance and of a fertilizer. The aci

corresponds more to the effects which can be observed on appl

tion of ethylene to various parts of plants. It is known tha

the plant itself produces, in various stages of development,

lene to a varying extent, particularly before and during the

ing process of the fruits, and at the end of the vegetation p

as the abscission of the fruit and leaves occurs. Since the

lation of ripening

463.5

34,26 7 71 and of fruit and leaf abscission by chemical substances is of the greatest commercial significance for the cultivation of fruit, citrus fruits, pineapples and cotton, compounds have-been

sought with which such effects might be obtained without damage being caused to the treated plants. Various classes of substances have thus meanwhile become known with which it was possible for certain of these effects, with regard

to growth regulation, to be achieved; Lhe sphere of action of these substances in no way corresponds, however, to that of ethylene. Compounds which, under certain conditions, release

ethylene are known. Such compounds are relatively unstable under the effects of weather, because they are very susceptible to hydrolysis; or they are phytotoxic.

p-Halogen-ethyl-phosphonic acid derivatives are described in the South African Patent No. 68/1036 as active substances regulating 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 p.-range below 5, the active substance concentrates have to be stabilised by the addition of acids. This acid addition limits, however, the range of application of these active substances with regard to phytotoxic effects. Furthermore, the storage of such sensitive active substance concentrates presents difficulties.

34, 267 /71 active substances, are Also known, as herbicidal cp. US-Patents Nos. 3,390,976 halogenalkyl-methyl-silanes, et al., J.Med. Chem. 2, and 3,390,977, and J.K. Leasure 949 (1966). p-Chloroetnyl-tris-(alkoxy)- silanes and p-chlo silanes and p-chloroethyl-acetoxy-dialkoxy et a been produced by F.W. Boye diacetoxy-alkoxy silanes have resp. 1386 (1952). J.Org.Chem. 16, 391 (1951), a-chloroethyl- The US-Patent 3,183,076 describes promotion which can be used for the methyldialkoxy-silanes, abscission, etc.% of germination power, leaf to new agents containing, The present invention relates the said as active substances, p-halogen-ethyl-silanes, or retarding effect new agents having a stimulating stages of development of on plant growth in the various of the the very good stability the plants. By virtue of conta: I, these agents must not active substances of formula agents, apart from the usual carriers, distributing against the effects of light and stabilisers protecting and acid stabilising additive, and oxidation, any additional of application. The therefore, an unlimited field are and the germination power vegetative plant growth and the blossom formation, influenced by the new agents; and the formation of the development of the fruit In the case of monocotyledons separating tissues promoted. and branching was observed an increase in tillering of growth in height. There with a simultaneous reduction of the support tissues of was moreover a strengthening

34 267 /71 formation the stalks in the case of the treated plants. The is very greatly reduced on of undesirable side shoots are' various types of plants. Furthermore, gum trees an effect stimulated to produce a greater latex discharge, have'shown which is of great commercial importance. Tests as well as that the rooting of seedlings and cuttings, is promoted. the development of tubers in the case of potatoes,

In addition, there occurs a simultaneous sprouting of

dormant rhizomes, which is particularly important

in the case of various perennial weeds such as be couchgrass, Johnson grass and cyperus, which can then The germination easily destroyed or suppressed by herbicides.

capacity of seeds such as, e.g. seed potatoes and

legumes is promoted with low concentrations, and

prevented with higher concentrations. Both these

effects are commercially important. A control of the

blossoming time and of the number of blossoms is

possible in the case of many ornamental and cultivated

plants. This effect is an especially important factor

in connection with pineapples. If all the trees or shrubs

blossom simultaneously, 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 also shown that in the case of fruit trees

there occurs a thinning of blossom and fruit. Furthermore,

there is obtained, e.g. with apples, pears, peaches,

7 463.569

34,267 /71 and tomatoes, bananes and pineapples, an acceleration As a improvement of fruit ripening and colouration. the result of the development of separating tissues, appreciably separation of fruit and leaves is rendered with more easy. This has great commercial significance

respect to mechanical harvesting, e.g. of citrus the fruits or cotton. With high concentrations,

defoliation of ornamental plants such as chrysanthemums, also obtained. rhododendrons, carnations and roses.is

The extent and the nature of the action are on dependent on the most diverse factors, particularly stage of the time of application with regard to the

development of the plant, and on the application depending on concentration. These factors vary, however, Thus, for the type of plant and on the desired effect. entire growth example, lawns will be treated during the the intensity period; ornamental plants, of which, e.g. before and number of the blossoms are to be increased, of which the development of the blossom setting; plants utilised, after fruit is to be sold, or in some other way of time before blossoming or at an appropriate interval the active the gathering of the crop. Application of

substances is effected by the use of solid or liquid above the agents, these being applied to parts of plants into the ground, to the surface of the soil, as well as soil itself. The preferred method is the application

-8 463

34,26 7 71 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. can The plant growth regulating action of the new agents often be positively influenced by the addition of organic or

inorganic acids and bases acetic acid or sodium carbonate).

It was determined in the case of citrus fruits

oranges that the abscission of fruit is appreciably easier after application of the active substances of formula I. Various active substances were sprayed,

in the form of solutions in concentrations of 0.2% 0.4%,

on to branches, well hung with fruit, of various

orange trees. The tests were evaluated after 14 days according to the method developed by W.C. Wilson and C.H. Hendershott, cp. Proc. Am. Soc. Hort. Sc. 123-129 (1967). The test consists of measuring the force in kg required for the abscission of the fruit.

9 463 569

34.267/71

Active substance: Concentration force in kg

2-chloroethyl-tris-(ethoxy)- 0.2 silane 0.47.

2-chloroethyl-tris- (octyloxy)- 0.2 3.7 silane 0,4

2-chloroethyl-tris-(benzoxy)- 0,2 silane 0.4

2-chloroethyl-tris-Cdodecyloxy 0.2 4,7 silane 0.4 7 1.1

8.6 Control

The fruit hanging on the tree'-could be so easily detached that no measurernen was possible.

34.267 /7-

Equally good and significant results were obtained

using agents containing the following compounds:

2-chloroethyl-tris-(2'-chloroethoxy)-silane, 2-chloroethyl-tris-[butenyl-(2')-oxyl-silane, 2-chloroethyl-tris-[propenyl-(2')-oxyl-silane, 2-chloroethyl-tris-(3'-chlorobutenyl-(2')-oxyl-silane, 2-chloroethyl-tris-(octadecyloxy)-silane, 2-chloroethyl-tris- (butynyl-(2')-oxyl-silane, 2-chloroethyl-tris-hexynyl-(3')-oxyl-silane, 2-chloroethyl-tris-(6'-chlorohexyloxy)-silane, 2-chloroethyl-tris-(4'-methoxy-benzoxy)-silane, 2-chloroethyl-tris-(2',4'-dichlorobenzoxy)-silane, 2-chloroethyl-tris-(4'-chlorobenzoxy)-silane.

It was observed on bean-leaf segments that the

leaf abscission is facilitated and promoted by formation

of separating tissues. Segments of bean-leaves of the type "Tempo" were immersed in a solution of 0.002%. of active substance; in the case of each active substance, 4-8 segments were left for 6 days under controlled conditions in the active substance solution. The numbzr of abscissions which had occurred (i.e.

contraction or necking of the stalk on the leaf-side of the abscission zone) was determined 3.5 and 6 days after commencement of the treatment. The assessment was made on the

basis of a 1 9 scale of values, whereby the value 9 corres-

ponds to 0 abscissions and the value 1 to 8 absoissions.

4 6 3.5 69

34, 267 /7, Evaluation aft Active substance Evaluation 6 days 1. j 2.

2-bromoethyl-tris-1 11

(benzoxy) -si lane

2-chloroethyl-tris-I chlorobenzoxy) -silane

1 (octadecyloxy)53.lafle

2-bromoethyl-tris 1 1 Ibutenyl- '-oxy I1-silane

4t 1 1 2-chloroethyl-.tris-( methoxypheloxy) silane

2-chioroethyl-tris-1 11 (carbobutoxyflethoxY)- silane

Comparable-and significant values. were obtained

using agents containing the following compounds:

2-bromoethyl-tris- (ethoxy)-silane, 2-broinoethyl-tris-(hexyloxy) -silane,

2-bromoethyl- tris- (4'-chlorobenzoxy) -silane, 2-bromoethyl-tris-(octadecyloxy)-iln~j 2-brornoetliyl- tris-[!propynyl- -oxy) -silane,

2-chloroethyl-tris Ipropynyl- (2')-oxyl -silane 2-chloroethyl-tris-(octyloxy) -silane,

34,26 7/71 2-chloroethyl-tri-(benzoxy)-silane,

2-chloroethyl-tris-(1'-carboethoxyethyloxy)-silane, 2-chloroethyl-tris-13'-chlorobutenyl-(2')-oxyl-silane, 2-chioroethyl-tris-[butenyl-(2')-oxyb-silae, 2-chioroethyl-tris-propenyl-(2')-oxybsilae, 2-chloroethyl-tris-[butinyl-(2')-oxyl-silane,

2-chloroethyl-tris-13',7'-dimethylocteny (7')oxy-silane,

2-chioroethyl-tris-(4'-methoxybenzox)-slae, 2-chloroethyl-tris- (hexynyl- )-oxyj -silane.

2-chioroethyl-(benzyloxy-diacetyloxy)-silal, 2-chloroethyl-(dioctyloxy-aetyloxy)-silane. The ripening acceleration was tested with tomato plants in the following manner: Tomato plants of the variety "Fournaise" are cultivated

outdoors under plastic sheets. After reacting a hight of m the shoot tips of the plants: are cut away. As the first fruits turn red the plants are sprayed with aqueous prepara- tions formulated from emulsion concentrates of the under- mentioned active substances. Four plants are each treated with 1,5 1 of a spray containing 2000 resp. 4000 ppm of active substance (ppm parts active substance per million parts of

solution). 10,14 and 17 days after treatment the ripe fruits on the three lowerst umbels are harvested. The sum of the yields (tomatos) thus obtained is given in the following table:

13 463569

34267 /71

Active substance quantity yield of ripe fruits from the employed three harvests (PPU1) weight in kg of total harvE

2-chloroethyl-tris- 2000 41,05 61,2 (octyloxy)-silale 41000 5,76 71,5

2-chloroethyl-tris7 2000 5,66 73,7 (benzyloxy)-silale 4000 6,26 75,9

2-chloroethyl-tris- 2000 5,92 85,2 -chlorobutelyl- )-oxy)-silane 41000 6,50 841,3

2-chloroethyl-tris- 2000 5,03 63,41 (butenyl-(2' )-oxy)- silane 4000O 6,o6 7503

2-chioroethyl-tris- 2000 5,50 70,6 (41'-methoxybenzyl- oxy)-silane 41000, 7,30 87,7

2-chloroethyl-tris- 2000 3,37 62,9 (1'-chlorobenzyl- oxy)-silane 41000 6,80 82,41

2-chloroethyl-tris-I 2000 5,32 7, (hexinyl-(3')-OXY)-1 10059182 silane 40 ,48,

untreated control j 3,411 52,0

The resin flow comparable with the latex discharge

or gum trees was evaluated with damson trees in the follo- wing manner: Segments of the bark are cut out from the bough s of

12 year old dams on trees (Prunus domestica). A 10% active

substance solution (10 parts active substance, 20 parts xylene, 70 parts castor oil) is then applied to the undamaged

surface of the boughs just above and below the above mnentio- ned incisions, each treatment being repeated on 41different trees.

-141 463.1

34. 267 71 4 Weeks after said treatment the exuded resin is

removed and weighed. The following table gives the average

weight of collected resin per treated bough in grams.

Active substance Grams resin

2-bromoethyl-tris(ethoxy)- silane 0,37

2-chloroethyl-tris(4'-me- thoxyphenoxy)-silane 1,81

2-chloroethyl-tris(propinyl- (2')-oxy)-silane 0,53

2-chloroethyl-tris(4'-chloro- benzyloxy)-silane 0,52

2-chloroethyl-tris(hexinyl- (3')-oxy)-silan 0,85

control (untreated) 0

Agents according to the invention are 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. Water-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

463 5 69

34.267 /71 substance in these agents is 0.5

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, ground

limestone, Attaclay, dolomite, diatomaceous earth,

precipitated silicic acid, alkaline-earth silicates, mica sodium and potassium aluminium silicates (feldspar and

calcium and magnesium sulphates, magnesium oxide, ground

synthetic materials, fertilisers such as ammonium sulphate,

ammonium phosphate, ammrnonium 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- as sulphonic acids with phenol and formaldehyde, as well

alkali, a-rmonium and alkaline-earth metal salts of

ligninsulphonic acid, also alkylarylsulphonates, of alkali metal salts and alkaline-earth metal salts

dibutylnaphth'alencsulphonic acid, fatty alcohol sulphates

such as salts of sulphated hexadecanols, heptadecanols,

i6 16463

.34, 267 71 alcohol octadecanols, and salts of sulphated fatty methyl tauride, glycol ether, the sodium salt of oleyl ammonium ditertiary acetylene glycols, dialkyl dilauryl and alkaline-earth chloride, and fatty acid alkali-metal metal salts. To these mixtures may also be added additives non-ionic, stabilising the active substance, and/or which, for anion-active and cation-active substances, the active substances example, improve the adhesiveness of and on plants and on parts of plants (adhesives (wetting agglutinants), and/or ensure a better wettability the following: agents). Suitable adhesives are, for example, (methyl cellulose, olein/lime mixture, cellulose derivatives glycol ethers carboxymethyl cellulose), hydroxyethylene 15 ethylene oxide of mono- and dialkylphenols having 5 radicals per molecule and 8 9 carbon atoms in the alkali metal and alkyl radical, ligninsulphonic acid, glycol alkaline-earth metal salts thereof, polyethylene ethers ethers (carbowaxes), fatty alcohol polyglycol and having 5 20 ethylene oxide radicals per molecule

8 to 18 carbon atoms in the fatty alcohol moiety, oxide, condensation products of ethylene oxide, propylene condensation polyvinylpyrrolidoncs, polyvinyl alcohols, as latex products. products of urea/formaldehyde, as well sieved The active substances are so mixed, ground, that and strained with the above mentioned additives powders the solid constituent in the case of wettable

-17- 463569

34.267 /71 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, dimethylsulphoxide, and mineral oil fractions boiling in the range of 1200 to 3500. The solvents must be practically odourless, non-phytotoxic, 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 following 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

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 o

about 0.1 mm; for scattering agents from about 0.075 mm

46 3:

34.267 71

to 0.2 mm; and for granulates 0.2 mm or coarser. The concentra-

tions of active substance in the solid preparations are from to All the mentioned active substance concentrates may also con- tain agents stabilising against the effects of light, and anti- oxidants.

Granulate The following substances are used for the preparation of a granulate: parts of 2-chloroethyl-tris-(2'-chloroethoxy)-silane, 0.25 parts of epichlorohydrin, 0.25 parts of cetyl polyglycol ether, 3.50 parts of polyethylene glycol ("CARBOWAX" Registered Trade Mark), 91 parts of kaolin (particle size 0.2 0.8 mm).

The active substance is mixed with epichlorohydrin and the mixture dissolved in 6 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 subse- quently evaporated in vacuo.

19 463569

34. 267 71

Wettable Fowder

The following constituents are used for the preparation

of a) a 40%, b) a 50%, c) a 25%, and d) a

wettable powder:

a) 40 parts of 2-chloroethyl-tris-(octyloxy)-silane,

parts of sodium lignin sulphonate,

1 part of sodium dibutyl-naphthalene sulphonate,

54 parts of silicic acid;

b) 50 parts of 2-chloroethyl-tris-(dodecyloxy)-silane, parts of alkylaryl sulphonate ("Tinovetin parts of calcium lignin sulphonate, 1 part of Champagne chalk/hydroxyethyl cellulose mixture (1 1),

parts of silicic acid,

14 parts of kaolin;

c) 25 parts of 2-chloroethyl-tris-(4'-methoxy-benzoxy)" silane,

parts of the sodium salt of oleylmethyl tauride,

parts of naphthalenesulphonic acid/formaldehyde condensate,

parts of carboxymethyl cellulose,

parts of neutral potassium aluminium silicate,

62 parts of kaolin;.

d) 10 parts of 2-chloroethyl-tris-(4'-chlorobenzoxy)-silan,

3 parts of a mixture of the sodium salts of saturated fatty alcohol sulphates,

4 6. 6

34.267 71

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 concentration. Such suspensions are employed, e.g. for the removal of undesired side shoots, for the tillering of lawns, and for the rooting of seedlings and cuttings, etc..

21 463.569

34.267/,71 Emul. S ion _concC'nf-.ate

The following constituents are mixed together to

produce 257% emulsion concentrates:

a) 25 parts of 2-chloroethyl-tris-(benzoxy)-silane, parts of a mixture of nonylphenclpolyoxyethylene and calcium-dodecylbenzele suiphonate,

parts of xylene;*

b) 25 parts of

parts of a mixture of nonylphenolpolyoxyethylene and calcium-dodecylbelzele suiphonate,

parts of cyclohexanone.

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

-22- 463

34.267 /71 Certain of the p-halogen-ethyl-silanes embraced by et all, formula I have already been described [cp. F.W. Boye

The A-bromo-ethyl-silanes of formula I, wherein X represents bromine, are new compounds.

Furthermore, A-chloro-ethyl-silanes of the more

restricted formula II

R1

Cl CH2 CH 2 Si R' (II)

Y

are also new compounds not described hitherto.

The symbols in formula II of the new compounds have

the following meanings:

Y represents chlorine or the radical -OR

RI', R 2 and R each represent, independently of each other, an alkyl radical an alkyl radical having 6 to 18 carbon atoms, alkoxy- substituted by halogen, alkoxy, alkenyloxy, alkylthio, radical carbonyl, phenoxy, cycloalkyl, by a heterocyclic

and/or di- and trialkylammonio, an alkenyl or halogenalkenyl a phenyl radical radical, an alkynyl, a cycloalkyl radical, halogen- optionally mono- or polysubstituted by cyano, alkyl, a alkyi, alkoxy, alkylthio, alkanoyl and/or alkoxycarbonyl, by alkyl, benzyl radical optionally mono- or polysubstituted R1', R 2 and alkoxy and/or halogen; one or more of the symbols

R may also represent the group-CO-R wherein R4 stands for

an alkyl, alkenyl or alkynyl radical, a halogenalkyl or radical substituted halogenalkenyl radical, an alkyl or alkenyl

463.569

34.267/71 phenyl can be substituted by by cycloalkyl or phenyl, whereby for an alkoxyalkyl, an alkoxy- alkyl, alkoxy and/or halogen, or phenyl radical, the latter carbonylalkyl, a benzoylalkyl lower alkyl or lower alkoxy, optionally substituted by halogen, radical; R 1 and R 2 or for a 5- or 6-membered heterocyclic -COR4 together with the adja- also with the signification of Si-containing saturated or un- cent atoms, can also form a

saturated heterocyclic ring system. in formula II, straight- By alkyl radicals are meant, 6 to 18 carbon atoms. chain or branched radicals having branched alkyl radicals Especially straight-chain and the alkyl moiety of alkoxy, having 1 to 8 carbon atoms form or alkoxycarbonyl sub- alkylthio, di- and trialkylammonium phenyl radical. stitutes of an alkyl radical or of the these are alkyl In the case of halogenalkyl radicals, which can be radicals having 1 to 6 carbon atoms, and/or bromine. An substituted by fluorine, chlorine by halogen has alkenyl radical optionally substituted radical 3 to 8 3 to 18 carbon atoms, and an alkynyl

carbon atoms. atoms form the Alkenyl radicals having 3 to 6 carbon By cycloaliphatic alkenyl moiety of alkenyloxy radicals. cycloalkyl and radicals are meant mono- and polycyclic 3 to 12 carbon atoms. cycloalkenyl radicals having according to the The new A-halogen-ethyl-silanes by reaction of a P-halogen- present invention are produced III: ethyl-trichlor-silane of formula

463

34, 26 7 /71 X CH2 C12 Si (1)3. (III)

with three equivalents of an acid of formula IV:

R4 C OH (IV) IS'.

0

or of a carboxylic acid anhydride of formula V:

R4 C 0 C R4

0 0

to give a compound of formula VI:

X CH2 C2 Si (0 C R) 3 (VI); II

0 and, optionally, by stepwise exchange 'of one, two or three

of the radicals

0 C 4

0

by radicals of alcohols of the formulae VII, VIII, IX

R'101 (VII)

R'3 0H (VIII) R'3oH (IX).

25 463 .569

34.267 1/7 If, in the starting compound of formula III X represents ex- bromine, also low molecular alkanols may be used for.the

chage of the radicals -0-CO-R4 in formula VI. If no one of the radicals R1 R2 and R i' identical with is

C R

0

can then the new 0-halogen-ethyl-silanes of formulae I and II

be produced according to a variant of the process by reaction

of a p-halogen-ethyl-trichloro-silane of formula III with one,

two or three equivalents of one of the alcohols of the

formulae VII, VIII or IX; however, if p-bromo-ethyl-trichloro-

silane is the starting material, also low molecular alkanols

having less than 6 carbon atoms, may be used for the reaction.

X in formula III represents chlorine or bromine;.

R4 in formulae IV and V has the meaning given under formula I;

and RI', R 2 and R in formulae VII, VIII and IX have the

meaning given under formula II.

As in the reaction according to the invention,

the exchange of the 3 chlorine atoms of the starting compound

of formula III occurs stepwise, it is clear that intermediates

i.e. dichloro- and monochloro-silanes of formulae Cl l012 X CH2 CH2 Si and X CH2 CH2 Si OR1 \OR1 OR2 (b)

can be isolated during the synthesis or as impureties from

the crude final product.

The compounds are embraced by the general

26 4635

34.26 7 171 also biological, plant growth formulae I and II and show

regulating activity. out in the presence The process is preferably carried are inert to the of solvents and/or diluents which particularly suitable, reactants. Aprotic solvents are hydrocarbons, e.g. such as, e.g. aliphatic and aromatic toluene, xylene, halogenated hexane, cyclohexane, benzene, ethylene, carbon hydrocarbons such as chlorinated also ethers tetrachloride, chloroform, chlorobenzene, ether, and ethereal compounds such as diethyl tetrahydrofuran, etc.. it is also possible for To obtain a complete reaction, carboxylic acid anhydrides the alcohols, carboxylic acids and when used in excess, as employed as reactants to serve, solvents or diluents. in some cases Furthermore, it can be necessary to the reaction mixture. to add an acid-binding agent in particular, tertiary Suitable for this purpose are, e.g. triethylamine, amines such as trialkylamines, dialkylanilines, etc.. pyridine and pyridine bases, in the range of The reaction temperatures are few 0 duration can be between a 0 to 100 C; the reaction and depends to a great extent minutes and several days, employed. on the reactivity of the alcohols to illustrate the The following examples serve invention. Listed in the Sprocess according to the

463.5 69

34,267/71 attached tables are.further new 0-halogen-ethyl-silanes of formulae I and II produced in the manner described in the examples. The temperatures are given in the examples in

degrees Centigrade, and the pressure in Torr.

Example 1

a) An amount of 40.8 g of 2-chloroethyl-trichlorosilane is dissolved in 71.5 g of acetic acid anhydride, and the solution allowed to stand at room temperature

for 21 hours in a closed vessel. The reaction product is concentrated in vacuo to obtain 44.6 g of 2-chloro- ethyl-tris-(acetyloxy)-silane, 85 88°/0.1 Torr,

1.6687. (Compound 1)

Calculated Found

C 35.8 36.0

H 4.8 4.7

Cl 13.20 13.4

Si 10.4 10.5

28 463.56

34. 267 71

b) An amount of 26.9 g of 2-chloroethyl-tris-(acetyloxy)- silane is dissolved in 40 ml of absolute benzene. To the solution are added at 50 550, within 60 minutes,

10.8 g of benzyl alcohol in 20 ml of absolute benzene. Stirring is carried out for 4 1/2 hours at 50 The reaction mixture is concentrated in vacuo, and 14.3 g of 2-chloroethyl-(benzyloxy-diacetyloxy)-silane 0 125 1270/0.001 Torr, n 1.4840. are obtained, (Compound 2) Calculated Found

C 49.3 49.4

H 5.4 5.4

Cl 11.2 11.7

Si 8.9 8.9

Example 2 An amount of 26.9 g of 2-chloroethyl-tris-(acetyloxy)- in 40 ml silane, obtained according to example la, is dissolved of absolute benzene; to this solution are then added at 50 in 20 ml of O within 60 minutes, 21.6 g of benzyl alcohol at absolute benzene. Stirring is carried out for 4 1/2 hours vacuo to 55°. The reaction mixture is concentrated in obtain 20.2 8 of 2 -chloroethyl-(dibenzyloxy-acetyloxy)-silane,

164 1660/0.005 Torr, nD5 1.5218. (Compound 3).

Calculated Found

C 59.3 59.4

H 5.8 5.6

C1 9.7 10.2

Si 7.7

29 463.569

34. 267 171

Exa mpte-a

An amount of 10.5 gof 2-chloroethyl-tricIh1orosilane ether; to is dissolved in 150 ml of absolute diethyl to within this solution are then added at and following minutes, 22.7 g of 4-chlorobenzyl alcohol, g of absolute this, in the course of 30 minutes, 12.6 ether. Stirring pyridine dissolved in 50 ml of absolute and the mixture is carried out for a further hour at 00, then refluxed for 18 hours. The reaction mixture is filtered, the filtrate in vacuo. washed twice with water, dried, and concentrated In this manner are obtained 23.5 g of 2-chloroethyl-tris- 2000 2100/0.01 Torr, (4'-chlorobenzoxy)-silane, nD =1.5636. (Compound 14).

Calculated Found

C 53.5- 53.4

H 4.3 4.3

Cl 27.5 27.8

Si 5.4 5.6

34,267 /71

Exar.ole 4

An amount of 16.9 g of 3-chlorobuten-(2)-ol is dissolved in 150 ml of absolute diethyl ether. The solution is

cooled to -10* to -50 and 12.6 g of absolute pyridine

are added; at the same temperature is then added dropwise,

within one hour, a solution of 10.5 g of 2-chloroethyl-

trichlorosilane in 50 ml of absolute diethyl ether.

The mixture is stirred for one hour at for 2 hours

at room temperature, and for 18 hours with refluxing.

The reaction mixture is afterwards filtered, the filtrate

quickly washed with ice-cold water, dried, and concentrated

in vacuo. Thus obtained are 21.5 g of 2-chloroethyl-

tris-I3'-chlorobutenyl-(2')-oxyl-silane, 1450 1500/

0.05 Torr, n0 1.4912. (Compound

Calculated Found

C 41.2 41.6

H 5.4 5.4

Cl 34.8 34.9

Si 6.9 6.6

31 463569

34, 26 7/71 Example 5 (Production of an intermediary product)

An amount of 59,4 g of 2-chloroethyl-trichloro-silane

is dissolved in 750 ml of absolute diethylether. To the obtair

solution is then added at to -100, within 1 hour, a solu-

tion of 34,9 g of hexanol-(l) and 23,7 g of absolute pyridine

in 250 ml of absolute diethylether. The mixture is then

stirred for 12 hours at room temperature, filtered and the

filtrate concentrated by evaporation in vacuo. After fraction-

ated distillation, 39,2 g of 2-chloroethyl-(hexyloxy-dichloro)

silane are obtained; 69-720/0,1 Torr.

Calculated Found

C 36.5 36.3

H 6.5 Si 10.7 11.0

Example 6 An amount of 59,4 g of 2-chloroethyl-trichloro-silane

is dissolved in 750 ml of absolute diethylether. To the ob-

tained solution is then added at to -10o, within 1 hour,

a solution of 69,7 g hexanol-(l) and 47,5 g absolute pyridine in 250 ml of absolute diethylether. The mixture is then

stirred for 12 hours at room temperature, filtered and the

filtrate concentrated by evaporation in vacuo. After fraction-

ated distillation, 32,5,g of 2~4e3'e-(dihexyloxy-chloro)-

silane are obtained; 97-1020/0.001 Torr; n2 1.4423.

(Compound 6).

S42 6356

34,2 67 /n Compounds of formula

0 R X C11 2 .2 Si -0 12 R

0 13 R

Table I

TT Physical data No. I. R 1 =R2 R3 B.P./Torr; nD

Ethyl Ethyl 83 -40 /14i Hexyl 145-501/O,6l Octyl, 165-70,1/O,O01 Octyl 165-70"/0:005 Dodecyl -10. Dodecyl b 1,4582 Octadecyl, 33-360 Octadecyl 35-360 2-Chloroethyl B. 123-260/0, 001 6-Chlorohexyl 210-15'/0,03 2-Methoxyethyl B. 103-1050/0, 2-Ethoxye thyl 122-1250/0,005 2-Butyloxyethyl -D 1,41495 2-Al lyloxyethyl 10-5O0/0,01 2-Ethylthioethyl 20P. 20= 1,4895 19520/,0

3- Phenylpropyl NO 1 53,40 2-Phenoxyethyl D~ 1,5466 2-Propenyl 95-1000/0,2 2-lButenyl 110-15'/0,2 2-Butenyl 3, 7-Di:nethyl-2-0Cte-. n2 0 1,4+707 fl D 2-Propinyl 0k0 I J-.

33 463569

34.267 /7,

No. x Physical data R1 R2 R I B.P./Torr; nD

31 2-Propinyl B. P. 115-200/0,005

32 3-Hlexinyl B. P. 170-50/0,005 B.P.: 145-500/0,005 33 _3-Chloro-2-butefyl 20 34 3-Phenyl-2-propefyl 1,5832 DO- 3-Phenyl-2-propenyl no 1,5882 1,4696 36 3-Cyanoethyl. 37 Ethoxycarbofyl- 20_ 1,4496 methyl DD 38 1Ethoxycarbonyl- B. P. 0 154-158 /0,3 (1-methyl)-methyl 39 Butoxycarbonyl- 20 1,4480 methyl DD Cyclohexyl 165-1700/0,001

41 Cyclohexylmethyl 180-1900/0,001

42 Cyclohexylmethyl "D -D 1,4833

43 Benzyl 190-2000/0,001 0 44 Benzyl nD 1,5612 4-Chlorobenzyl 200-200/0,01

46 4-Chlorobenzyl n2O 1,5757 47 4-Methoxybenzyl n20 1,5224 48 2,4--Dichlorobenzyl n20 1,6637 49 4-Methylbenzyl nBO 1,5433 Phenyl nBO 1,5623

51 4-Chiorophenyl n8O 1,5769 3-Chlorophenyl nr7 1,5262 52 q7 1,5257 53 3,4-Dichlorophenyl 54 3,5-Dichlorphenyl nb 0 1,5268

4-Bromophenyl n27 1,5418

4-Methoxyphenyl n20 1,5620 56 .n2 57 4-Methoxyphenyl D 1,5641 DD &0 1,5590 58 3-Methoxyphefyl 4-Butyloxyphenyl 2O 1,5307 59 D 0 4-tert-Buty2.phenyl 75-770 3-Methylphefyl n27 1,5385 61 62 3-Methylphenyl nZO 1,5490 63 3, 4-Direthylphfly1 n27 1,4935

461

34.267 /7, Physical data No.j R1 R2 R3 B.P./Torr; D

3-Forrnylphefll Cl 9lolO11 14-Cyanophenyl Cl 14..Ethoxycarbonllphenll Cl Cl 65-700 .3-Ethoxycarbollphell

Cl 195-200/0,001

C1

"JCH2

Cl 2 1,5771

UICHF-

*25 1 4A727 Cl

463a569

34.267 /71

Table II

R1 R 2 =R 3 -C OR 4 Physical data No. X R4 is: Br 120-122'/0., 72 Methyl Cl 85 880/0, 73 M!ethyl 0 Cl 102-104 /0, 74 Ethyl Br 115-1250/0, Ethyl 20 1,4286 76 Pentyl Cl .2-440 77 Undecyl Br 44-470 78 Undecyl Hep tadecyl Cl 54-570 79 20 01 D 1,4484 2-Propenyl 24-27 0 Cl 81 1-Propenyl Br ,621 4= 82 2-Propenyl ClD- 1 ~201,4480 83 9-Decenyl Cl .120 1,4705 84 8,11-Heptadecadieflyl Cl -12D 1,4681 2-Cbloroethyl lBronopentyl Cl120 1,4513 86 1o-Bromodecyl Cl 49-500 87 Br 48-500 88 lO-Bromodecyl Cl 250 89 cis-2-Chloroethenyl Br 55-580 cis-2-Chlortethenyl Pheny line thyl Cl. 74-78 0 91 20-300 Phcnylrmethyl Br 92 35w390 2-Phenyl ethyl Cl 93 99-130 Cl 94 4-Ch1or phemnyh.thyl Cl 57-600 3-MethylphnyImethYl C! 98-1020 96 3- (4 ,e tho:yphclny) -ethyl C1 97 4- EthoxycarbofylbutYl 3-oxuobtyl- ci n420 1,4590 98 Dr .r20 =1,841 99 3-OxobuLyl

34. 267 /71

R 1 No. R2 R 4 is: R= -CO-R 4 X Physical data

73-750 100 5-Phenyl-5-oxo-pentyl Cl 101 2-Ethoxycthyl Cl 1,4365 Cl 58-600 102 3-Pheno-.:propyl Cl M. 1400 103 2,4-Dichlorophenoxyreth)4 Br 137-1380 2,4-'ichlorophenoxymethyl 2-(4 '-Chlorphcnyl)-1-ethenyl CL .105 Cl 128-1300 106 2-Phenyl-1-ethenyl Br 129-1310 107 2-Phanyl-1-ethenyl oS 2-(3',4'-Dichlorphenyl)-l- M.P.: 2350 ethenyl 2- (4 'Methoxyphenyl-l-eihenyl M.P.: 1780 109 20 Cyclohexylwe thyl 1,4494 110 DD Cyclohexylmetbyl .1,4592 111 1,578. 112 Cyclohexyl Cyclopropyl 1,4515 113 20 114 3-Cyclohexenyl 1,4740 3-Cyclohexenyl fO 1,1807 115 116 2-Cyclopentonyl n20 1,4680

117 2-Cyclopentenyl 20 118 Prienyl nD 1,5632 M.P.: 2330 119 4-Chlorophenyl 120 4_Methoxy-phenyl M.P.: 177-1780

121 4-Methyiphefyl M.P.: 165-1700

122

123 123-125O

124 123-1250

37 46 .5569

34. 267 /794

.Table III

3 CO-R X Physical da ta 4 No. R1 -R R4 is:

MIethyl C1 B.p.:126 270/0.0 126 Benzyl Methyl Br 140-1430/0,( 127 Benzyl methyl1 Cl 164-1660/0,1 128 Befizyl Benzyl methyl C1 62-6511/0,01 129 Ethyl :104-11O0/0,O' Pen tyl Methyl. Br 130 PentY 1 Methyl. C1 B.P. 115-l20/0,0' 131 Octyl methyl Cl :150U520 /0,0 132 octyl octyl thyl Cl 2- Butynyl 2-Butynyl I~:e 1.33 2-Buteflyl viMethyl Cl 94-989/0,06 1L34 2-Butenyl 135 4-Chlor- Ethyl ci n2O. 1,4940 benzyl 136 4- Chlor Ethyl Br nD 1,5042 benzyl 137 3,7-Dime- R thyl-7- Ethyl Cl 1,4525 octenyl 138 4-AItethoxy- Ethyl CI r20 14890 benzyl

-38-4

34, 267 /71

Table TV

R2 x anion physical No. R1 R3 data

CHO Hexyl Cl Cl 0 M.P. :25-35" Hexyl 139 N, -CR -CRH CR3H CHR3 Cl CIP n0 1,5212 140 313\0 Benzyl Benzyl N-CH 2 -CH2 C3 H

Table V (Compounds wherein R and R together with the adjacent ring system). atoms, form a Si-containing heterocyclic

No.' active substanCe Physical data

CHCH ,-OH 2 ,\613 2 115 -2 0/ ,0 14CH 3/iY 2 O'C-Cl-CH

/CH 25 22 n 5233 142 >O-SiCH-7CH2-C

002F

CO-0 OC5HI1i

143

co-oCCH-

144 BCO-0,Si-H 2 CHi- 1

-39 463.556

.If 34,267 /71

active substance Physical data No.

I145 ij-CH2-H2-1 N -0 2 -C

Co

0Si-CH2-CH2C

C6 13

4 0- 463

34261 /71

Table V3I conpounds of the formula:

Cmn. RviR Pysical data

6 n-hexyl C1 nD 1.4423 20 1.5192 147 3-phenyiprOPYl Cl nf 20 1.4678 148 2-butenyl C1 nD 20 1.4764 149 3-he22dnyl Cl nDf 20 1.4836 150 cyclohexyl. Cl

cyclohexylmethyl C1 1.4766 151

benyl Cl 20 1.5266 152 20 1.5552 153 4-chlorobenzyl flfl 20 1.5455 4-qnthoxy-benzyl Cl nD 154 20 1.5343 155 4..methylbeflyl Cl. PDl 20 1.5486 156 3-methoxypheflyl C1

C1 n20 1.5372 157 3-inethylphefll

n-dodecyl Cl 1.4564 158 20

nA-Octy]l Cl 1."479 159 20 Br nfl 1.4532 160 n-hexyl

6-chiordohxyl Cl. 1.4707 161

2-ethoxYethYl Cl 87-920/0-001 162 Cl 680/14 163 methyl b .p. 1-phenylethyl Cl 1340/0.001 164 C1 90-94/0.001 165 2-metboyethyl I 462.68

34, 267 /71

In a test in Italy, on olive trees of the variety "CORA- TINA" a number of branches were sprayed, about 1 week before their expected harvest, with aqueous compositions of the listed active ingredients. The concentration of the active

ingredients in the spray liquid was 1000, 2000 or 4000 ppm and each treatment was repeated twice. On each tree, some branches were not treated and served as control branches. The tests

were evaluated 4 days after spraying, by shaking the treated and untreated branches by hand. The olives which fell were counted as percent of the initial number of olives on the corresponding branches, and the results are given in the following table:

compound tested amount applied in ppm NO. 1000 2000 4000

147 50%

148 45%

149 80

150 95% 100%

155 15%

156 60% 100%

158 12%

162 100% 100%

165 30%

Control 2-8%

463.5 69

Claims (1)

1. 34,267 /71

   THE CLAIMS DEFINING THE INVENTION ARE AS FOLLOWS:-

   1. Composition for the regulation of plant growth, comprising ingredient at besides carriers and distributing agents as active

   least one S-halogen-ethyl silane of formula I O R

   X CH2 CH 2 Si O R2 Y

   chlorine or wherein X represents chlorine or bromine; Y represents of each the radical -OR 3 R 1 R 2 and R 3 represent, independently

   other, alkyl radicals; alkyl radicals substituted by halogen, phenoxy, cyano, alkoxy, alkenyloxy, alkylcarbonyl, halophenoxy, radicals cycloalkyl, alkylthio, alkoxycarbonyl, by heterocyclic alkynyl and/or di- and tri-alkylammonio; alkenyl, halogenalkenyl, polysubstituted and cycloalkyl; phenyl radicals optionally mono- or formyl, phenoxy, by cyano, alkyl, halogenalkyl, alkoxy, alkylthio, mono- alkanoyl and/or alkoxy-carbonyl; benzyl radicals optionally one or more or polysubstituted by alkyl, alkoxy and/or halogen; of the symbols R 1 R 2 and R 3 can also represent the group

   CO R4

   radical, a halo- wherein R4 stands for an alkyl, alkenyl or alkynyl

   genalkyl or halogenalkenyl radical a cycloalkyl or cycloalkenyl radical, an alkyl or alkenyl radical substituted by cycloalkyl and/ or phenyl, whereby phenyl can be substituted by alkyl, alkoxy

   or halogen; an alkoxy-alkyl, an alkoxycarbonylalkyl, a benzoylalkyl

   radical; a phenyl radical optionally substituted by halogen, C 1 -8

   alkyl

   .43 463.5 69

   34. 267/71

   or 1-ewe-alkoxy; a heterocyclic 5- or 6-membered radical;

   R 1 and R 2 also with the signification of -CO-R 4 together

   with the adjacent atoms, can also form a silicium-contanining

   saturated or unsaturated heterocyclic ring system.,

   2. Composition according to claim 1, comprising as active

   ingredient at least one A-halogen-ethyl-silane of formula Ia

   X CH2 CH2 Si (OR) (Ia)

   wherein X represents chlorine or bromine, and R represents an

   optionally halogen-substituted alkyl or alkenyl radical, an

   alkynyl radical, or the benzyl radical optionally mono- or

   polysubstituted by lower alkyl, lower alkoxy and/or halogen,

   together with carriers and distributing agents.

   3. Composition according to claim 1 comprising as

   active ingredient at least one 0-halogen-ethyl-silane of

   formula

   OR 1 X- CH CH2 Si OR2 (Ib) OR3

   wherein X represents chlorine or bromine, R1, R 2 and R

   independently of each other, represent alkyl radicals; alkyl

   radicals substituted by halogen, alkoxy, alkenyloxy, phenoxy,

   cycloalkyl, alkylthio, alkoxycarbonyl and/or trialkylammonio;

   alkenyl, halogen alkenyl, alkynyl and cycloalkyl; phenyl

   radicals optionally mono- or polysubstituted by cyano, alkyl,

   halogenalkyl, alkoxy, alkylthio, alkanoyl and/or alkoxycarbonyl

   benzyl radicals optionally mono- or polysubstituted by alkyl,

   alkoxy and/or halogen; one or more of the symbols Rl, R 2 and

   Ri can also re'presnt the group AA 46356

   34.267 (71 CO R4

   or alkynyl radical, wherein R stands for an alkyl, alkenyl

   radical; an alkyl or alkenyl a halogenalkyl or halogenalkenyl whereby phenyl can be substitu- radical substituted by phenyl, an alkoxyalkyl, an alkoxy- ted by alkyl, alkoxy and/or halogen; radical, or an alkyl radical carbonylalkyl, a benzoylalkyl

   substituted by cycloalkyl. of plant growth which 4. Process for the regulation

   or parts of plants or the growth comprises treating plants of formula substrate of plants, with 0-halogen-ethyl-silanes

   I of claim 1. 4, for promoting the Process according to claim for acceleration of ripening abscission of fruits and leaves, and latex discharge of trees and for promoting the resin plants or parts which comprises treating the corresponding of formula I of claim thereof with p-halogen-ethyl-silanes 2. 1 and of formula Ia of claim

   New A-bromoethyl-silanes of formula 6.

   /OR1 Br CH 2 CH 2 Si I OR 2 Y

   1. meanings given under claim wherein Y, R 1 and R 2 have the of formula 7. New A-chloroethyl-silanes /OR Cl CH CH2 Si (II) I OR21 Y

   radical -OR and R', wherein Y represents chlorine or the R 2 and R 3 in R2 and R have the meaning given for R l 463.569

   34,267 /71 claim 1, with the proviso that if RI', R 2 R and R 4 stand for unsubstituted alkyl radicals, those alkyl radicals

   comprise 6 to 18 carbon atoms.

   8. Process for the production of 1-bromo-ethyl-silanes

   of formula OR /o01 Br CH CH Si 2 2 INOR2 Y

   wherein Y, R 1 and R 2 have the meanings given under claim 1,

   which comprises reacting A-bromoethyl-trichlorosilane with at

   least 2 equivalents, preferably with 3 equivalents of an acid of formula IV

   R4 COOH (IV)

   or of an acid anhydride of formula V

   R4 CO 0 CO R (V)

   in order to obtain a compound of formula

   Br CH2 CH 2 1i (0-CO-R 2

   Y'

   wherein Y' represents chlorine or the radical -O-CO-R and,

   optionally replacing stepwise one, two or all three present

   radicals -0-CO-R4 by the radicals of alcohols of formulae

   R1OH, R20H and/or R OH, wherein R 1 R2 and R have the

   meanings given in claim 1, with the exception of the signi-

   fication -CO-R1

   9. Process for the production of A-bromoethyl-silanes of formula

   463.569

   34.267 7i OR1 Br CH CH 2 Si 2 I2 OR Y 2

   under formula I wherein Y, R 1 and R2 have the meanings given -COR 4 which of claim 1 with the exception of the meaning

   comprises reacting p-bromoethyl-trichloro-silane with in 3 equivalents total at least two, preferably with in total R20H and/or R OH, of one or more alcohols of formulae R 1 OH,

   wherein R 1 R 2 and R have the meanings given in claim 1,

   with the exception of the signification -COR

   Process for the production of new A-chloroethyl-

   silanes of formula II /OR'

   Cl CH 2 CH 2 Si OR 2 (II)

   Y

   and R 1 wherein Y represents chlorine or the radical -OR3

   R2 R and Rk are defined as in claim 7, which comprises

   reacting p-dhloroethyl-trichloro-silane with at least two of an acid of equivalents, preferably with 3 equivalents

   formula IV R4 COOH (IV)

   or of an acid anhydride of formula V

   R CO 0 CO R (v)

   in order to obtain a compound of formula

   Cl CH2 CH2 Si (O-CO-R4)2 2 21

   463.569

   34. 267771

   arein Y' represents chlorine or the radical -0-CO-R one, two or all three i optionally replacing stepwise of alcohols of esent radicals -0-CO-R4 by the radicals Ri', R 2 and R 3 rmulae R 1 'OH, R2'0H and/or R 'OH, wherein the exception of ve the meanings given in claim 7, with e signification -COR 1 Process for the production of new A-chloroethyl-

   lanes of formula II /OR1

   Cl- CH2 CH2 Si -OR 2 (II)

   Y

   -OR3 and R1 terein Y represents chlorine or the radical of and R are defined as in claim 7 with the exception

   ie meaning COR 4 which comprises reacting A-chloroethyl- preferably with ,ichlorosilane with in total at least two, alcohols of formulae i total 3 equivalents of one or more R2 and are wherein R 1 L'OH, R2'OH and/or R 'OH, ifined as above.

   1971 DATED this TWENTY-NINTB day of SEPTEMBER, AGRIPAT S.A.

   Patent Attorneys for the Applicant SPRUSON FERGUSON

   463.5 69