DE2331185A1 - MEANS OF REGULATING PLANT GROWTH - Google Patents

Description

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509 Leverkusen. Bayerwerk

Dii / ed

II a Jt 8, June Ί / j

Means for regulating plant growth

The present invention relates to the use of partially known heterocyclic sulfonium salts for Regulation of plant growth.

It is already known that certain 2-haloethyl-trialkylammonium salts, in particular (2-chloroethyl) trimethyl ammonium chloride, plant growth regulating properties (see U.S. Patent 3,156,544). The effect of these compounds, however, is mainly at low application rates and concentrations, not always satisfactory.

It has been found that the partially known heterocyclic sulfonium salts of the formula

(D

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in which ^

R represents optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl or aralkyl optionally substituted in the aryl part, A ^ represents one equivalent of an anion and X represents oxygen or the groups Jf-R ¹ R "A ^ or S ^ -R ¹ " ,
in which

A0äie has the meaning given above, R ^! and R "are the same or different and represent lower alkyl and

R " ^{1 stands} for the same radicals as R and moreover, together with R, can stand for the radical -CHg-CI ^ -,

have strong plant growth regulating properties.

Surprisingly, the heterocyclic compounds according to the invention show Sulphonium salts have a considerably higher plant growth-regulating effect than that from the prior art known (2-chloroethyl) trimethyl ammonium chloride, which is the chemically closest active ingredient of the same type of action is. The substances that can be used according to the invention thus represent a valuable addition to technology.

The heterocyclic sulfonium salts to be used according to the invention are clear from the general formula I Are defined. In formula I, R preferably represents optionally substituted straight-chain or branched alkyl with 1 to 4 carbon atoms. Preferred substituents are hydroxy, methoxy, methylcarbonyl, alkoxycarbonyl with 1 to 4 carbon atoms in the alkyl part and halogen, especially chlorine and bromine. Furthermore, R preferably represents alkenyl having 2 to 4 carbon atoms, alkynyl with 2 to 4 carbon atoms, also for cycloalkyl with

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3 to 12 carbon atoms, in particular 3 to 7 carbon atoms, and also preferably for aralkyl optionally substituted in the aryl part by halogen, such as chlorine, with 1 to 4 carbon atoms in the alkyl part and 6 to 10 carbon atoms in the aryl part. It stands preferably for halide, in particular chloride, bromide and iodide, and also for tetrafluoroborate. In addition, A ^ preferably represents alkyl sulfate, especially methyl sulfate or ethyl sulfate. X preferably represents oxygen or the grouping W ^ it'R ¹¹ A ^ j in which R 'and R ^M, independently of one another, preferably represent alkyl having 1 to 4 carbon atoms and A ^e preferably represents the anions already mentioned above. Furthermore, X preferably stands for the grouping S -R ⁿⁱ AS in which R " ^{1 stands} for the same radicals which are also preferably suitable for R, and in addition, together with R, can stand _{for the radical -CH 0 -.}

As examples of the active ingredients which can be used according to the invention are mentioned in detail:

1,4-dimethylsulfonia-cyclohexane-dimethosulfate, 1,4-diethylsulfonia-cyclohexane-difluoroborate, 1,4-diethylsulfonia-cyclohexane-diethosulfate, 1,4-Dipropylsulfonia-cyclohexane-dibromide, 1,4-dibenzylsulfonia-cyclohexane-dichloride, 1,4-Dicy clopentylsulfonia-cy clohexan-d ij od id, 1,4-di- (ß-chloroethyl) -sulfonia-cyclohexane-dichloride, 1,4-divinylsulfonia-cyclohexane-dichloride, 1,4-Dipropargylsulfonia-cyclohexane-dibromide, 1,4-disulfonia-bicyclo- (2,2,2) -octane-dibromide, 1-methylsulfonia-4-oxacy clohexane-chloride, 1-methylsulfonia-4-oxacy clohexane methosulfate, 1-Benzylsulfonia — 4-oxacyclohexane chloride, 1-methylsulfonia-4-dimethylammonia-cyclohexane-dimethosulfate.

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Some of the substances which can be used according to the invention are known (see. Reports 9, 696-7o2 (1886); Reports 67, 1142 1144 (1934); J. Org. Chem. 1 ±, 704-718 (1946)). However, their use to regulate plant growth has not yet been described.

Some of the substances according to the invention are new, they can but can be produced in a simple manner by methods known in principle. For example, you get it when one cyclic sulfur compounds of the formula

(II)

in which

Y stands for oxygen, sulfur or the group in which R ^{1 is} lower alkyl,

with a compound of the general formula

R ^IV - Z (III)

in which

IV
R stands for optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, optionally substituted aralkyl in the aryl part or for the triethyloxonium ion and

Z stands for halogen, alkyl sulfate or tetrafluoroborate stands,

optionally in the presence of a solvent at temperatures between ^{0 0} C and 130 ° C.

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The compounds of the formula II used as starting materials are known or can be prepared by known processes (cf. J. Chem. Soc. H9, 1249-1256; Synth. 2_, (4), 183 (197o)). The following are specifically mentioned as examples of the compounds of the formula II:
1,4-dithiane,
4-oxa-thiacy clohexane,
N-methylthiomorpholine.

The compounds of the formula III which are also required as starting materials are also known. As examples are specifically mentioned: methyl iodide, ethyl bromide, propyl chloride, Allyl chloride, propargyl chloride, benzyl chloride, 4-chlorobenzyl chloride, 2,4-dichlorobenzyl chloride, chloroacetone, Chloroacetic acid and its esters, chloromethyl ether, chloromethyl naphthalene, Dimethyl sulfate, diethyl sulfate and triethyloxonium-tetrafluoroborate.

The solvents used in the reaction described above are preferably lower alcohols, for example methanol, chlorinated hydrocarbons such as methylene chloride and Chloroform, also dimethylformamide, acetonitrile, acetone or water.

In the preparation of the substances according to the invention by the above process, the reaction products fall after the end of the process Reaction either directly crystalline or they can be removed by adding a solvent in which they are insoluble, deposit in an oily or crystalline state. The crystalline products are isolated - if necessary after the previous one Concentrate the reaction mixture - by simply suctioning off. Additional cleaning is possible by falling over.

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If the reaction products are obtained as oils, so do so isolation by first separating the phases and then cleans the oil by treating it with activated charcoal in an aqueous or alcoholic solution.

In the compounds which can be prepared by the above process, if Y ^ is chloride, bromide or iodide, vary the anion by reacting with silver salts.

The 1,4-disulfonia-bicyclo- (2,2,2) -octane-dibromide can also be found in addition to the method described in the literature (cf. J. Org. Chem. U_, 704-718 (1946)) in prepare the way that tris-2-hydroxyethyl-sulfonium chloride is treated at temperatures between 100 ° C and 14o ° C with aqueous hydrobromic acid. The product is appropriately isolated by concentrating the reaction mixture under reduced pressure and removing impurities from the remaining crystalline residue by washing with methanol. The tris-2-hydroxyethylsulfonium chloride required as a starting material is already known (cf. J. Chem. Soc. 1951 , 224-236).

The active ingredients according to the invention reach into the physiological Occurrences of plant growth and can therefore be used as plant growth regulators.

The various effects of the active ingredients depend on the essentially from the time of application, based on the stage of development of the seed or the plant as well of the concentrations used.

Plant growth regulators are used for various purposes related to the stage of development of the plant.

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The growth of the plants can be strongly inhibited with the substances according to the invention. Such an inhibition of the Vegetative growth plays an important role in cereals, as this reduces or completely prevents storage can be. At the same time, the substances according to the invention achieve consolidation of the stalk.

In many crops, the inhibition of vegetative growth allows a denser planting of the culture, so that a More yield, based on the floor area, can be achieved. Another mechanism of increasing the yield with growth inhibitors is based on the fact that the nutrients to a greater extent benefit the bloom and fruit formation, while the vegetative growth is restricted.

However, the substances according to the invention can also be used to promote vegetative growth. This is from great benefit when the vegetative parts of the plant are harvested. However, vegetative growth can be promoted also lead at the same time to a promotion of generative growth, so that z. B. more or larger fruits come to training.

The active ingredients according to the invention can also be used to accelerate or delay fruit ripening and the coloration of the fruit to enhance. A temporal concentration of the fruit ripeness is also possible. The effects you want can be achieved by varying the concentrations of the active ingredients used and by applying them to different levels Achieve times during the development of the plant.

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The active compounds according to the invention can be used in the customary formulations such as solutions, emulsions, suspensions, powders, pastes and granulates. These are in produced in a known way, e.g. by mixing the active ingredients with extenders, i.e. liquid solvents, liquefied gases under pressure and / or solid carriers, optionally with the use of surface-active substances Agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents. In case of Using water as an extender, organic solvents, for example, can also be used as auxiliary solvents. The main liquid solvents that can be used are: aromatics, such as xylene, toluene, benzene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or Methylene chloride,

aliphatic hydrocarbons such as cyclohexane or paraffins, e.g. petroleum fractions, alcohols such as butanol or glycol as well as their ethers and esters, ketones, such as acetone, methyl ethyl ketone, Methyl isobutyl ketone or cyclohexanone, strong polar solvents such as dimethylformamide and dimethyl sulfoxide, and water; with liquefied gaseous extenders or carrier substances are meant liquids which are gaseous at normal temperature and under normal pressure are, for example, aerosol propellants such as halogenated hydrocarbons, e.g., Freor; as solid carriers: natural Powdered rock, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic ones Ground rock, such as finely divided silica, aluminum oxide and silicates; as an emulsifier and / or foam generator Medium: non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, Polyoxyethylene fatty alcohol ether, e.g. alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, Aryl sulfonates and protein hydrolysates; as dispersants: e.g. lignin, sulphite waste liquors and methyl cellulose. The active compounds according to the invention can be present in the formulations as a mixture with other known active compounds.

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The formulations generally contain between 0.1 and 95 percent by weight of active ingredient, preferably between 0.5 and 9o? I.

The active ingredients can be used as such, in the form of their formulations or the use forms prepared therefrom, such as ready-to-use Solutions, emulsions, foams, suspensions, powders, pastes and granulates can be used. The application happens in the usual way, e.g. B. by pouring, spraying, atomizing, scattering, dusting, etc.

The active ingredient concentrations can be in a larger range can be varied. In general, concentrations of from 0.05 to 2,96, preferably from 0.01 to 0.5 #, are used.

Furthermore, 0.1 to 100 kg, preferably 1 to 10 kg, of active ingredient are generally used per hectare of soil area.

For the application time, the use of the growth regulators applies is made in a preferred period, the exact delimitation of which depends on the climatic and vegetative conditions.

The following examples show the activity of the substances according to the invention as growth regulators, without excluding the possibility of further applications as growth regulators.

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Example A ^ "

Growth retardation / barley

Solvent: 10 parts by weight of methanol

Emulsifier: 2 parts by weight of polyethylene sorbitan mono-

laurat

For the production of an appropriate preparation of the active substance
1 part by weight of active ingredient is mixed with the stated amounts of solvent and emulsifier and made up to the desired concentration with water.

Young barley plants, 25-3o cm high, are sprayed to runoff with the active ingredient preparation. After 4 weeks, the increment is measured and the inhibition of growth is measured in 56 of the increment
of the control plants calculated. It means 1oo 56 den
Growth cessation and growth corresponding to that of the untreated plants.

Active ingredients, active ingredient concentration and results run out Table A below.

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Table A.

Growth retardation / barley

Active ingredient

Concentration in ppm

Growth. inhibition in

Water (control)

(known)

I000 5oo

35 1o

H ₅ C

H ₃ C

y \ /

I000 5oo

5o 35

Cl

5oo

3o

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Example B Λ

Inhibition of growth / wheat

Solvent: 10 parts by weight of methanol

Emulsifier: 2 parts by weight of polyethylene sorbitan mono-

laurat

To produce an appropriate preparation of active ingredient, 1 part by weight of active ingredient is mixed with the stated amounts of solvent and emulsifier and the mixture is made up with water
desired focus on.

Young, 25-30 cm high wheat plants are sprayed to runoff with the preparation of the active ingredient. After 4 weeks, the increase is measured and the inhibition of growth in $ of the increase
of the control plants calculated. It means $ 100> the stagnation of growth and 0 96 a growth corresponding to that
of the untreated plants.

Active ingredients, active ingredient concentrate and results run out Table B below.

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Inhibition of growth / wheat

Table B.

Active ingredient

Concentration of growth inhibition in ppm in 96

Water (control)

*) ₃ ci <

(known) 1ooo
5oo

60 4o

H ₅ C

5-CH ₃ 2 er 1000
5oo

80 60

Cl

5oo

4o

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Example O 4H

Promotion of growth / beans

Solvent: 10 parts by weight of methanol Emulsifier: 2 weight of steep polyethylene-sorbitan-mono-

laurat

For the production of an appropriate active ingredient preparation 1 part by weight of active ingredient is mixed with the stated amounts of solvent and emulsifier and made up with water the desired concentration on.

Young bean plants about 10 cm high are treated with the active ingredient Preparations sprayed until they drain. After 14 days, the growth of the untreated plants is compared determined for the untreated control plants.

Active ingredients, active ingredient concentration and results run out Table C below.

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Table C Growth promotion / beans Active ingredient

Concentration limbs

flow

in ppm in ^ the

control

Water (control) OK

C ₂ H ₅ -S

5oo

5oo

+ 25

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example 1 f

Ψ —NE

36/4 g (0.2 mol) of triethyloxonium tetrafluoroborate are added to a solution of 12.0 g (0.1 mol) of 1,4-dithiane in 300 ml of methylene chloride at 20 ° C. and the mixture is left to stand for several hours at room temperature. The excreted particulate matter is then filtered off with suction and recrystallized from methanol for further purification. 29.9 g (85% of theory) of 1,4-diethylsulfonia-cyclohexane-di-tetrafluoroborate with a melting point of Ho ⁰ C. are obtained.
analysis

Ber .: for CgH ₁₈ F ₈ "DC OT
2 2 ' 3 9 5 , 2 H 18 2 5 Found: 27 4? 5 , 3 H 18 3 5 Example 2 έ C ί p 6 C i S

A solution of 52 g (0.5 mol) of 4-oxa-thiacyclohexane in 50 ml of acetonitrile is mixed with 71 g (0.5 mol) of methyl iodide and heated to 50 ° C. for 2 hours. After cooling, 100 ml of ether are stirred into the reaction solution and the product which separates out is separated off. This gives 73.8 g (60? 6 of theory) of colorless 1-Methylsulfonia-4-oxacyclo-hexanjodid melting point of 188 ⁰ C.

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analysis

Calc .: for C ₅ H _{1 2} JOS 24, 4th C. 4, 5 5 51 , 6 y Found: 24, 6th C. 4, 3? 51 , 9 y Example 3 i H S J i H S J

CH

63 g (0.5 mol) of dimethyl sulfate are added to a solution of 23.4 g (0.2 mol) of N-meth.yl-morph.oline in 150 ml of dimethylformamide and the mixture is heated to 130 ° C. for 10 hours. After cooling to room temperature, 200 ml of ether are stirred into the reaction solution and the oil which separates out is separated off. 61 g (83,96 theoretical) of 1-methylsulfonia-4-dimethy 1-ammonia-cyclohexane-dimethosulfate are obtained in the form of a viscous oil. analysis

Calc .: for C ₉ H _{21 NOgS 3} 5.2 £ N 36.0 # S Found: 5.8 56 N 35.8 <f> S

Example 4

A mixture of 2o2,5 g (1 mole) of tris-2-hydroxyäthylsulfoniumchlorid and 600 ml of 48 $ hydrobromic acid is heated to 12o ° C ^ hours. During the reaction, a mixture of 1,2-dibromoethane, 1,4-dithiane and water distills off. After the subsequent cooling, the reaction mixture is concentrated in vacuo and the remaining residue is freed from adhering impurities by washing with methanol. 119.5 g (72? Έ of theory) of 1 ^ -Dlsulfonia-bicyclo-

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(2,2,2) -octane-dibromide of melting point 193 ° C (decomposition).

analysis

Calc .: for C ₅ H ₁₂ Br ₂ S ₂ 23.4 # C 3.9 $ H

Found: 23.4 96 C 3.9 # H

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Claims (5)

Patent claims ^ 'n), agent for influencing plant growth, characterized by a content of heterocyclic sulfonium salts of the formula A® (I) in which R is optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl or aralkyl optionally substituted in the aryl part, A ^ - / f (jp _e j [ _{n is} equivalent of an anion and X is oxygen or the groupings ipk'R "αΘ or ^ SR" · A0 is in which A ^) has the meaning given above, R ¹ and R ^{w are} identical or different and are for stand lower alkyl and rhi stands for the same radicals as R and in addition, together with R for the rest - can stand. 2. Means for inhibiting the growth and influencing the habitus of higher plants, characterized in that that one heterocyclic sulfonium salts according to claim 1 used as active ingredients. Le A 15 o67 - 19 - 409883/1313 3. A method for influencing plant growth, characterized in that there are heterocyclic sulfonium salts according to claim 1 can act on the plants or their habitat. 4. Use of heterocyclic sulfonium salts according to Claim 1 for influencing plant growth. 5. A process for the preparation of an agent for influencing plant growth, characterized in that one heterocyclic sulfonium salts according to claim 1 mixed with extenders and / or surface-active agents. Le A 15 o67 - 2o - 409883/1313