SUBSTITUTED OCTYL-PIPERIDINIUM CHLORIDES, BROMIDES OR IODIDES

AN 61o2/8 The present invention relates to ammonium compounds.

More particularly, the invention is concerned with ammonium compounds and a process for the manufacture thereof. The invention is also concerned with agents for the regulation of plant growth containing one or more of said ammonium compounds, a process for the preparation of said agents and a method for the regulation of plant growth by means of said agents.

lO The ammonium compounds provided by the present invention have the following general formula î' ®J-k RI (I) wherein R1 represents a lower alkyl group containing i-4 carbon atoms, a lower alkenyl group containing 2-4 carbon atoms or a lower alkymyl group containing 2-4 carbon atoms, R2, R3 and R$ each represent a lower alkyl group containing 1-4 carbon atoms or R2 and R$ together with the carbon atom to which they are attached form a 5-membered or 6- -membered alicyclic ring and X represents chlorine, bromine or iodine.

According to the process provided by the present invention, the ammonium compounds of formula I hereinbefore are manufactured oz/23.zo.zg? - 2 - lO a) reacting a compound of the general formula R R S R4 (II) ,' wherein R2 , R3 and R4 have the significance given earlier, with a compound of the general formula RIX (iii) or , wherein R1 and X have the significance given earlier, b) reacting a compound of the general formula RI , wherein RI has the significance given earlier, with a compound of the general formula R R 2 3 wherein R2, R3, R$ and X have the significance given earlier.

(IV) (v) According to embodiment a) of the present process, a compound of formula II is reacted with an appropriate lower alkylating, lower alkenylating or lower alkynylating agent.

lO 10.36165 For this purpose, a compound of formula Il is dissolved in a lower alkanol (preferably methanol or ethanol), an ether (e.g.

dìoxane), a dì(lower alkyl) ketone (e.g. acetone), dimethylformamide, a chlorinated hydrocarbon (e.g. chloroform, carbone tetrachloride or methylene chloride) or a hydrocarbon (e.g.

benzene or toluene), preferably in ethanol or benzene. A thus-prepared mixture is then reacted with the desired lower alkylatìng, lower alkenylating or lower alkynylating agent.

As such agents there may be used the usual lower alkylating, lower alkenylating or lower alkynylating agents such as, for example, the chlorides, bromides or iodides. The reaction is advantageously carried out at a temperature between O°C and 60°C, preferably at room temperature. The pressure is not critical; the reaction can be carried out in an open vessel.

Preferred ammonium compounds of formula I hereinbefore are 1-(3,7-dimethyloctyl)-l-methylpiperidinium iodide, 1-(3,7- -dimethyloctyl)-l-(2-propenyl)piperìdiniumbromide and 1-(3?7- -dimethyloctyl)-l-(2-propynyl)pìperidiniumbromìde.

In the process provided by the present invention, the preferred starting materials are compounds of formula II. The compounds of formula II are expediently prepared by catalytically hydrogenating a compound of the general formula (vl) wherein R2 , R3 and R4 have the significance given earlier.

In carrying out this catalytic hydrogenation, a compound of lOælç5 formula VI is dissolved in a lower alkanoi, preferably ethanol, and treated with the catalyst, preferably 5% palladium-carbon or platinum oxide. The mixture is expediently hydrogenated at room temperature with occasional cooling until hydrogen is no longer taken up. The catalyst is filtered off and the filtrate evaporated. The residue is distilled over a Vigreux column in a high vacuum.

The agents for the regulation of plant growth provided by the present invention contain an effective amount of one or more of the mmonìl/m compounds of formula I hereinbefore in association with a compatible carrier material. These agents are particularly useful as post-emergence and pre-emergence plant growth regulators. However, the post-emergence plant growth regulating activity is predominant.

The expression "plant growth regulator" as used in this specification denotes, for example, a compound which either retards or stimulates the growth of main or side branches or shoots of plants. Such a compound is capable of influencing the flower formation, the onset of flowers, the shoot or branch formation, the parthenocarpy, the falling of fruit and/or leaves and the ripening of fruit and/or leaves with or without the prior application of fertilisers. In addition, such compounds have an effect and an influence on the transport of substances within the plants, for example a stimulation of the latex flow and/or the metabolism or, for example, an increase in the sugar content within the plant, etc.

1O36165 In shrubs, for example, this regulatìng activity produces a retardation of the growth in height with concomitant stimulation of the side-growth.

The ammonìum compounds of formula I hereinbefore are particularly useful ìn agents for the re llatìon of plant growth.

The compounds have, in fact, a pre-emergence plant growth regulating activity, but they are especially useful when they are used as post-emergence plant growth regulators.

lO The ammonium compounds of formula I hereinbefore are especially active in and against the following plants (especially young plants):

a) Cereals such as corn, rice, wheat, rye, barley, oats etc; b) Trees and shrubs such as fruit trees (e.g. apple, pear, peach, cherry and lemon) as well as cocoa, tea, coffee, banana, gum, olive and walnut; c), Ornamental plants such as privet, hornbeam, white cedar, juniper, rose, azalea, chrysanthemum, poinsettia, cyclamen, pyracantha, forsythia, magnolia, petunia and bromeliad; d) Field plants such as, for example, cotton, soya bean, groundnut, tobacco, flax, sugar beet and pineapple; e) Vegetables such as Solanaceae (e.g. tomatoes), legumes, pumpkins, melons etc; f) Berries such as strawberries, bilberries, raspberries, blueberries, blackberries and redcurrants.

10S616,5 , The ammonium compounds of formula I hereinbefore are also useful since they reduce the pruning of vines in a vineyard and the harmful effects of general contamination (polution) on the plants is reduced to a large extent or even illìminated (e.g. the effect of ozone or sulphur dioxide).

lO In order to achieve a homogeneous distribution of the ammonium compounds in the present plant growth regulating agents, the ammonium compound or 8mmonìum compounds is/are mixed with conventional adjuvants, modifiers, diluents or conditioning agents which are customary in plant growth regulating agents and the resulting mixture is formulated into solutions, emulsions, emulsifiable concentrates, dispersions, dusts, granulates or wettable powders.

Plant growth regulating agents in the form of liquid formulations suitable for direct spraying can be prepared, for example in the form of aqueous solutions - whenever possible - or as solutions in solvent mixtures which contain, for example, acetone, methanol and dìmethylformamide in a ratio of 90:8:2 (volume/volume).

Emulsifiable concentrates containing 25-50°% or more of ammonium compound of formula I depending on the solubility thereof can be prepared using suitable solvents such as N- -methylpyrrolidìne, dimethylformamide etc. Surface-active substances (e.g. wetting agents, dispersants, emulsifiers etc) are added in a sufficient amount to produce a formulation having the desired characteristics.

lO 10,36165 Various application forms can be better adapted to the various purposes for which the present ammonium compounds may be used if substances which improve the dispersion, adhesion, penetration and resistance to rain are added. Such substances include fatty acids, waxes, resins, wetting agents, emulsifiers, mineral oils, vegetable oils, binding agents etc. In a similar manner, the biological spectrum of the present ammonium compounds or plant growth regulating agents may be greatly broadened by the addition of substances having bactericidal, herbicidal or fungicidal properties or by the addition of fertilisers, chelate-forming agents and other plant growth regulators.

Examples of herbicides and plant growth regulators which can be present in the agents provided by the present invention are:

2,2,dichloropropionìc acid, N-(4-amìnobenzenesulphonyl)methylcarbamate, 2-chloro-4-ethylamìno-6-isopropylamino-l,3,5-triazine, 4-chloro-2-oxobenzothiazolin-3-yl-acetic acid, 5-promo-6-methyl-3-(1-methyl-n-propyl)uracil, 3,5-dibromo-4-hydroxybenzonitrìle, D,N-ethyl-2-(phenylcarbamoyloxy)propionamide, N-(€-bromo-3-chlorophenyl)-N'-methoxy-N'-methylurea, methyl 2-chloro-9-hydroxyfluorene-9-carborylate, N'-4-(4-chlorophenoxy)-phenyl-N,N-dimethylurea, isopropyl-N-(3-chlorophenyl)-carbamate, 2,3,5 6-tetrachloroterephthalic acid dimethyl ester (DCPA), 2,$-dichlorophenoxyacetic acid, lO 10,36165 4-isopropylamino-6-methyl camino-2-methyl thio-1,3,5- -triazine, n-butyl 9-hydroxyfluorene-9-carboxylate ,, ethyl ene, naphthoxyacetic acid, 3,6-dìchloro-2-methoxybenzoìc acid (+)-2-(2 4-dichlorophenoxy)propionìc acid 9,10-dìhydro-Sa, lOa-dìazonìaphenanthrene-2A N ' -( 3, $-dì chl o rophenyl )-N, N-dime thylurea, gìbberellic acid, indolylacetic acid indolylbutyrìc acid, $-hydroxy3,5-diiodobenzonitrìle, N ' -( 3,4-dìchlorophenyl )-N-me thoxy-N-me thylure a, ($-chloro-2-methylphenoxy)acetìc acid, 4- (4-chloro-2-methylphenoxy)butyrìc acid, (+-)-2- (4-chloro-2-methylphenoxy) propionic acid, N- (b enzo thì azol-2-yl )-N, N ' -dime thylure a, N ' - ( 3-chloro-4-methoxyphenyl )-N, N-dime thylure a, i, 2,3,6-t etrahydro3,6-dioxopyridazine, N' -( -chlorophenyl )-Ne-methoxy-N-methylure a, N' - (4-chlorophenyl)-N, N-dime thylure a, naphthylacetic acid, N-l-naphthylphthalamìc acid, 2,4-dichlorophenyl 4-nitrophenyl ether i, i ' -dimethyl-4,4 -bipyridylium-2A, 3-(m-tolylcarbamoyloxy)phenyl carbamste, 4-amino-3,5,6-trichloropicolinic acid, 4,6-bi s-isopropylamino-2-methyl thio-1,3,5-triazine, N-( 3,4-dichlorophenyl )-propionamide, l0 10æ1(;5 i sopropyl-N-phenyl carbam«2 t e, 5-amìno-4-chloro-2-phenylpyridazìn3 ( 2H )-one, N-dime thylamino succini c acid, 2-chloroethylphosphorus acid, tributyl-2,4-dichlorobenzyl-phosphonìum chloride, 2,4,5-tri chlorcphenoxypropionì c acì d, 2,3,6-trìchlorobenzoic acid, 2-chloro-4,6-bis-ethylamìno-1,3,5-trìazìne, sodium chloroacetate 2,4,5-trìchlorophenoxyacetìc acid, 5-chloro-6-methyl-3-t er t. butyluracil, 4-ethylamìno-2-methylthio-6-tert .butylamino-1,3,5- -triazine- (tert .butyryn), 2,3,5-trìiodobenzoic acid and 1 1,4-trime thyl-6-ì sopropyl5-propionyl-indane.

Examples of fungicides which may be present in the plant growth regulating agents provided by the present invention are:

2,4-dichloro-6-(o-chloranìline)-S-triazine, 2,4,5,6-tetrachloroisophthalic acid nitrile, p-dìmethylamìnophenyldiazo sodium sulphonate, 1,4-dìchloro-2,5-dìmethoxyb enz ene, manganese ethylene-bis-dithiocarbamate, zinc ethylene-bis-dithìocarbamate, coordination product from zinc and manganese ethylene- -bis-dithiocarbamate, methyl 1-(butylcarbamoyl)-2-benzimidazole carbamate, 2- (4-thiazol e )-benzimidazol e and ci s-N- [ ( t rìchloromethyl )-thìo ]-4cyclohexene-1,2- -dicarboximíde.

- lO - lO 1O36165 The amounts of Ammos compounds of formula I hereinbefore which can be used may be based on the results set forth hereinafter. However, it will be apprecìated that these results are not exhaustive and that, ìn addition, numerous other factors influence the amounts used. For example, the amount can vary not only between different species of plants but also within a specific species (e.g. depending on factors such as the size and the age of the plant), the particular ammonium compound used, the time of year, the type of soil and climatic conditions at the time of use such as the air temperature, light intensity, rain and wind. Furthermore, if the ammonium compounds or the plant growth regulating agents come into contact with the plant via irrigation of the soil, higher concentrations will be necessary since, with this type of use, the plant is indirectly treated in comparison with a direct treatment by application of the ammonium compound or plant growth regulating agent on to leaves and stems (e.g. by spraying).

Accordingly, the amount of ammonium compound present in the plant growth regulating agents varies according to the plants to be controlled, the amount required for application, the method of application, the particular ammonium compound used and the degree of regulation of plant growth which is desired. In general, the present agents contain less than 50% of ammonium compound in a ready-for-use spray form.

In principle, the amount of ammonium compound which is used is chosen so that an effective control of the plant growth is achieved. Accordingly, the choice of the minimum amount of - ll - lO 10,36165 ammonium compound used is governed by the minimum amount of ammonium compound which is able to effect the lower limit of growth retardation desired. The choice of the maximum amount of ammonium compound used is correspondingly governed by thor amount of ammonium compound which is able to bring about the upper limit of growth retardation desired. In the case of tomato plants, the criteria for an effective growth retardation are of such a nature that a dwarfed plant which has no loss in fruit quality or quantity is particularly desired. The parameters for an effective growth regulating activity in such plants ari retarded growth in height and increased or non- -retarded side-growth as a minimum effect and retarded growth in height and retarded side-growth as a maximum effect. The amount of ammonium compound corresponding to these criteria or bringing them about is determined by such aspects, for example, of the tomato plant. In order to achieve the greatest post-emergence growth regulating activity, amounts of 0.5 kg to 10 kg or more per hectare are used, these amounts being based on the weight of 8mmonìum compound. In a similar manner, the greatest post-emergence growth regulating activity is generally obtained using amounts which lie between 1 kg and kg or more of ammonium compound per hectare, these amounts being based on the weight of ammonium compound. A preferred range for spray solutions lies between 10 parts per million and 100,O00 parts per million depending on the plant species to be treated and the particular 8T, monium compound chosen.

An especially preferred amount generally lies between lO0 parts per million and 10,OOO parts per million.

3o A further advantage of the present ammonium compounds lies in the absence of both a lasting effect on the plants or lO 6165 a regulating activity which remains ìn the soil. The present ammonium compounds decompose slowly and there is accordingly a consequent reduction in activity. This effect has advantages since a) a short-term effect which may be lengthened by subsequent further treatment is produced; b) the normal growth behaviour of the plant re-occurs in step with the decrease in activity; and c) no harmful residues remain either on the plant or in the soil.

The duration of the retardation effect varies according to the partìcular ammonium compound used and other factors such as the type of plant treated, climatic conditions etc.

Although the ammonium compounds of formula I hereinbefore possess a plant growth regulating actìvity, they are virtually non-toxic to animals.

It will, of course, be appreciated that not all of the ammonium compounds of formula I are active against all plants.

Each of the ammonium compounds does, however, possess activity against a specific plant or plants and this activity is a function of the particular ammonium compound. As will be evident from the following, a particular advantage of the present invention is that the plant growth regulating agents posses pre-emergence and post-emergence plant growth regulating activity when used for the treatment of various plants, the range of plants being extremely wide. The growth regulating activity of the present ammonium compounds will be evident 10,16165 from the followìng micro-test for the determination of the post-emergence activity.

Several concentrations of ammonium compound are sprayed on to the plant so that a complete spray coating is obtained or the roots 8re watered with Just sufficient ammonium compound solution for the pot in which the plant is standing to hold without liquid being drained into the supporting dish for the pot (the amount required is previously determined in a blind test using water).

lO The ammonium compound is dissolved in water and the solution treated with 0.1% Tween In a treatment of the roots of Petunia hybrida of the "Furore" type, the height of the plant in comparison to an untreated control was measured after 5 weeks. The results are given in Table I hereinafter as a percentage reduction relative to the control. N-Dimethylamino-succinic acid hemihydrazide (Alar) was used as the standard.

Table I Compound i-( 3,7-Dimethyloctyl)-l-(2- -prop enyl )- piperidinium bromide Alar* Concentration Root treatment ppm type of % Reduction ,N 15oo appli cation ml per pot ml per pot * Trade Mark 10,.36165 In a treatment of the supraterranean plant parts of Chrysanthemum morfoliumusìng a complete spray coating, the side sprouting was measured after 60 days. The results are given in Table II hereinafter as a percentage reduction of growth of the side sprouting in comparison to an untreated control. N-Dìmethylamìno-succìnìc acid hemihydrazide (Alar) was used as the standard.

Table II lO Compound Concentration % Reduction ppm l-(3,7-Dimethyloctyl)- -l-(2-propenyl)- piperìdiniumbromide Alar 4OOO 40OO * Trade Mark 10,36165 The following Example illustrates the process provided by the present invention for the manufacture of the ammonium compounds of formula I hereinbefore.

Example lO 2883 g (12.8 mol) of tetrahydrogeranylpìperidine are introduced into a three-necked flask provided with a reflux condenser, stirrer and gas inlet tube. 2030 g (16.9 mol) of allyl bromide in ll.5 litres of absolute alcohol are added under an inert gas atmosphere and while stirring. The mixture is stirred at room temperature for 3 days. The mixture is then evaporated in a rotary evaporator and the residual, almost colourless, oil dried for 48 hours in a high vacuum.

There is thus obtained 1-(3,7-dimethyloctyl)-l- (2-propenyl)- pìperidinium bromide in the form of an almost colourless oil; n24 = 1.5243.

In an analogous manner, but using propargyl bromide in place of allyl bromide, there is obtained 1-(3,7-dimethyloctyl)-l-(2-propynyl)piperidinium bromide as a yellow oil; nD = 1.5165.

In an analogous manner, but using methyl iodide in place of allyl bromide, there is obtained 1-(3,7-dimethyloctyl)-l- -methylpiperìdinium iodide; melting point 1 °-136°C.

The starting material can be prepared as follows:

lO 2 40 g of piperidìne dissolved ìn 7 lìtes of low-boiling petroleum ether are added to a 20 litre reactìon flask provided with a stirrer, condenser, dropping fennel and drying tube.

The mixture is cooled to +5°C using an ice/methanol bath.

3927 g of geranyl bromide are now added dropwìse at 5@-lO°C over a period of 1 hour. The resulting mixture is stirred overnight without replacing the cooling bath and is then transferred to a 50 litre stirring vessel and stirred with litres of 1-N hydrochloric acid. The aqueous phase is extracted twice with 5 litres of low-boiling petroleum ether each time. The organic phases are combined, back-extracted twice with 2 litres of 1-Nhydrochloric acid each time and then discarded. The aqueous extracts are combined, made alkaline with ca 2 litres of concentrated sodium hydroxide solution and then extracted three times with 30 litres of low- -boiling petroleum ether each time. The extracts are each washed twice with 5 litres of saturated sodium chloride solution, dried over sodium sulphate and evaporated. The residue is distilled over a small Vigreux column in a high vacuum, there being obtained geranyl piperidine in the form of a yellowish oil; boiling point 0.8 = 95°-100°C" 3o 6000 g (27.15 mol) of geranyl piperidine are dissolved in 6 litres of alcohol and introduced into a 20 litre hydrogenation flask. 300 g of 5°% palladium-carbon are added and the mixture is hydrogenated at room temperature with occasional cooling until the hydrogen uptake comes to a standstill. The catalyst is filtered off and the filtrate evaporated. The residue is distilled in a high vacuum over a small Vigreux column. There is thus obtained tetrahydrogeranylpiperidine; boiling point 0.7 = 86°-88°C" 10,36165 The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

l) Ammonium compounds of the general formula RI xQ (T) fO wherein R1 represents a lower alkyl group containing 1carbon atoms, a lower alkenyl group containing 2-4 carbon atoms oì a lower alkynyl group containing 2-4 caleçon atoms, R2, R3 ud R4 each represent a lower alkyl group containing 1-4 carbon atoms or R2 and R4 together with the carbon atom to which they are attached form a 5--membered or 6- -membercd alicyclic ring end X repìesents chlorine, bromine or ìodine, 2) i- ( 5,7-Dimethylo ctyl )-l- (2-prop enyl )piperi dinium bromide, a compound of claim i.

3) l-(3,7-Dìmethylocty])-l-(2-prop yl)piperidinium bromide, a compound of claìm l.

l-( 3,7-Dìmethyloctyl )-le-methylpl peridinium iodide r a compound of claim l.

5) A process for the manufacturer of the ammonium compounds of formula I given in claim l, which process comprises a) reaoting a compound of the general formula R4/