DE2135623A1 - GROWTH REGULATORS - Google Patents

Description

2135623 FARBENFABRIKEN BAYER AG

»15. July 1971

LEVERK US EN-Bayerwerk Central area Patents, trademarks and licenses

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Growth regulators

The present invention relates to the use of chloroacetic acid amides, some of which are known, as growth regulators.

It has been known for a long time that chloroacetic acid amides have herbicidal properties (see, for example, German Patent 1014 380 ; Agricult. _Ao Food Chem. 4, 517 (1956) and 5, 30 (1957)).

From all previously known publications on compounds this group shows that these exert a killing effect preferentially on grass-like (monocotyledonous) plants, whereby the application is preferably carried out before the weeds germinate. Because of these properties, chloroacetic acid amides are used therefore so far only used as a weed control agent. Also chloroacetic acid furfurylamide, tetrahydrofurfurylamide and hexahydrobenzylamide should have analogous properties (see the above-mentioned references, as well as U.S. Patents 2,929,702 and 3,007,786).

It has now surprisingly been found that the partial known in the ring system saturated or unsaturated chlorine

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acetic acid amides of the formula I

CH ₂ -NC-CH ₂ Cl

in the

P.
Around

a CH ₂ group or an oxygen atom, a hydrogen atom, an alkyl, alkenyl or alkynyl group with 1 to 6 carbon atoms,

Hydrogen, lower alkyl groups, optionally substituted aralkyl groups or optionally substituted ones Mean aryl groups and means 0 or 1.

dampens growth on a large number of grassy plants work without damaging them or even killing them off completely.

According to the current state of knowledge, such an effect was not to be expected _9, especially since very similar known substances, such as the chloroacetic acid diallylamide used as a herbicide in practice, as well as the chemically very closely related chloroacetic acid hexahydrobenzylamide show no such effect.

Active ingredients ^ that dampen the growth of grass-like plants gain constantly increasing in importance. B. in ornamental lawns or on paths and roadsides so far mainly The maleic hydrazide used has considerable disadvantages. as A particularly serious disadvantage is the browning of the plants which occurs under the influence of the maleic acid hydrazide felt. The substances according to the invention, on the other hand, lead to a dampening of growth, without the overall status and the color of the plants to change. The substances according to the invention provide thus a valuable addition to technology.

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The substances according to the invention are unambiguous by the formula I. characterized. According to this, it is a question of chloroacetamides of saturated or unsaturated cyclopentyl or cyclohexyl methylamines and chloroacetamides of furfuryl and pyranylmethylamines, which can also be partially or fully hydrogenated in the heterocycle, d. H. so also to chloroacetamides from Di- and tetrahydrofurfurylamines and dihydro- and tetrahydropyranylmethy! Amines, which also have one to three alkyl groups as substituents in the heterocycle (preferably with up to four carbon atoms), aralkyl groups, preferably with 1-3 carbon atoms in the alkyl part and 1-3 aryl substituents on this alkyl part as well as (possibly by alkyl, alkoxy, j | Halogen or trifluoromethyl substituted) aryl groups. The aminomethyl group can be in 2-, 3- or 4-position to be bound to the heterocyclic ring.

Specific examples of the substances according to the invention include:

Chloroacetic acid-furfuryl- (2) -amide chloroacetic acid-4-isopropyl-furfuryl- (2) -amide 5-methyl-furfuryl- (2) -amide chloroacetic acid 5-butyl-furfuryl- (2) -amide chloroacetic acid-5-benzyl-furfuryl- (2) -amide

Chloroacetic acid 5- (3,4-dichlorobenzyl) -furfuryl- (2) -amide |

5-phenyl-furfuryl- (2) -amide chloroacetic acid Chloroacetic acid 5- (4-chloro-phenyl) -furfuryl- (2) -amide Chloroacetic acid 5- (4-methyl-phenyl) -furfuryl- (2) -amide Chloroacetic acid 5- (3-trifluoromethyl-phenyl) -furfuryl- (2) -amide Chloroacetic acid 5- (4-methoxyphenyl) -furfuryl- (2) -amide Chloroacetic acid 4,5-dimethyl-furfuryl- (2) -amide chloroacetic acid-jfuryl- (3) -methyjj-amide Chloroacetic acid-N-methyl-N-furfuryl- (2) -amide

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Chloroacetic acid-N-ethyl-N-furfuryl- (2) -amide Chloroacetic acid 2,3-dihydro-furfuryl- (2) -amide Chloroacetic acid 3,4-dihydro-furfuryl- (2) -amide Chloroacetic acid 4,5-dihydro-furfuryl- (2) -amide chloroacetic acid-tetrahydrofurfuryl- (2) -amide 5-methyl-tetrahydrofurfuryl- (2) -amide chloroacetic acid 5-benzyl-tetrahydro-furyl- (2) -amide chloroacetic acid Chloroacetic acid-jpyranyl- (2) -methyi-amide Chloroacetic acid-jpyranyl- (3) -methyl} -amide chloroacetic acid-jpyranyl- (4) -methyl-amide Chloroacetic acid J2,3-dihydro-pyranyl- (2) -methyl] -amide Chloroacetic acid-N-butyl-N- [2,3-dihydro-pyranyl- (2) -methylj -

Chloroacetic acid-N-allyl-N- {2,3-dihydro-pyranyl- (2) -methyij -

Chloroacetic acid - ^, 5-dimethyl-2,3-dihydro-pyranyl- (2) -methylamide Chloroacetic acid- ^, 4-dimethyl-2,3-dihydro-pyranyl- (2) -methyl-

Chloroacetic acid - ^, 6-dihydro-pyranyl- (2) -methy2-amide Chloroacetic acid betrahydropyranyl (2) methyl amide Chloroacetic acid, tetrahydro-pyranyl- (3) -methyi-amide

Chloroacetic acid-N-isopropyl-N-tetrahydro-pyranyl- (2) -methyj -

Chloroacetic acid 1,2,5,6-tetrahydro-benzylamide Chloroacetic acid 4-methyl-1,2,5,6-tetrahydrobenzylamide Chloroacetic acid-hexahydro-benzylamide chloroacetic acid-N-sec.butyl-N-hexahydrobenzyl-amide Chloroacetic acid-3,4-dichloro-hexahydrobenzyl-amide 3-chloro-4-methyl-hexahydrobenzyl-amide chloroesslgic acid

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Some of the substances according to the invention are known, for example chloroacetic acid-furfuryl- (2) -amide, chloroacetic acid-tetrahydrofurfuryl- (2) -amide, chloroacetic acid-5-methyl- and -5-benzylfurfuryl- (2) -amide, chloroacetic acid-5 -methyl- and -5-benzyltetrahydro-furyl- (2) -amide, chloroacetic acid-tetrahydropyranyl- (2) -methyl-amide, chloroacetic acid-tetrahydropyranyl- (3) -methyl-amide (cf. US Patent 2 929 702; Izv. Akad. Nauk Arm. SSR. Khim. Nauki ^ 4, 363 (1961); Chem. Abstr. 57, 11136 (1962), Bl. Boc. Chim. Fr. 1959 , 1393).

Insofar as compounds of the invention are not yet known λ, they can be prepared in known ways, preferably corresponding amines by reaction with chloroacetyl chloride. The amines required for this are either known or can also be prepared in known ways.

The active ingredients according to the invention intervene in the physiological Events 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 development stage of the seed or the plant as well as from

the concentrations used. (j

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

E * can be achieved that the budding of the buds is delayed, e.g. B. in areas that are endangered by Croatia Avoid damage from frost.

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The growth of shoots and roots can be inhibited by the active ingredients. So it is z. B. possible the growth of the fully developed. formed plant to inhibit very strongly or to cause dwarfism.

The growth inhibition at roadsides and roadsides is of economic interest. Furthermore, the frequency of grass clippings (Lawn mowing) can be reduced to lawns. The growth of woody plants can also be inhibited.

During the growth of the plant there may also be lateral branching be increased by a chemical break in the apikaid dominance. There is interest z. B. in the propagation of cuttings from plants. In a concentration-dependent manner it is however, it is also possible to inhibit the growth of the side shoots, e.g. B. to the tobacco plants after the decapitation To prevent the formation of side shoots and thus to promote leaf growth.

The transpiration rate can also be controlled with growth regulators Lower the plants to prevent dehydration damage.

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

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The formulations generally contain "between 0.1 and 95 percent by weight of active ingredient, preferably between 0.5 and 90 %."

The active ingredients can be used as such, in the form of their formulations or in the application fora prepared from it. like ready-made Solutions, emulsifiable concentrates, emulsions, suspensions, wettable powders, pastes, soluble powders,

I.

medium and. Granules are applied. It is used in the usual way, e.g. by spraying, atomizing, atomizing, Dusting * -scattering, smoking, gasifying., Pouring, Pickling or encrusting.

The active ingredient concentrations in the ready-to-use preparations can be varied over a wide range. In general, they are between 0.0001 and 10%, preferably between 0.01 and 1 % »

V *

The active ingredients can also be used with good success in the ultra-low-volume process (ULV), where it is possible to apply formulations up to 95% or even the 100% active ingredient alone.

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Depending on their intended use, the new active ingredients can be used in the usual formulations are transferred, such as solutions, Emulsions, suspensions, powders, pastes and granulates. These are prepared in a known manner, for example by mixing of the active ingredients with extenders, i.e. liquid solvents and / or carriers, optionally using Surface-active agents, i.e. emulsifying and / or dispersing agents, whereby e.g. in the case of the use of water as Extenders, optionally organic solvents as auxiliary solvents can be used. The main liquid solvents that can be used are: aromatics (e.g. xylene, Benzene). Chlorinated aromatics (e.g. chlorobenzenes), paraffins (e.g. petroleum fractions), alcohols (e.g. methanol, butanol), strongly polar solvents such as dimethylformamide and dimethyl sulfoxide as well as water; as solid carriers: natural Ground rock (e.g. kaolins, clays, talc, chalk) and synthetic ground rock (e.g. highly dispersed silica, Silicates); as emulsifiers: non-ionic and anionic emulsifiers such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g., alkyl aryl polyglycol ethers, alkyl sulfonates, and aryl sulfonates; as a dispersant: e.g. lignin, ' Sulphite liquors and methyl cellulose.

The active compounds according to the invention can be used in the formulations present in a mixture with other known active ingredients.

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(known) (known)

9 (known)

List of active ingredients

C ₂ H ₅

NC-CH ₂ Cl

I ₀ J-CH ₂ -NH-C-CH ₂ Cl

0 / V-

CH ₂ -NH-C-CH ₂ Cl

-CH ₉ Cl ²

CH

₀ JJ-CH ₂ -NH-O-CH ₂ Cl

k ₀ X- CH ₂ -NH-C-CH ₂ Cl

α O

H CH ₂ -NII-C-CH ₂ CL

C 1 -CH _{2 -CH 2} -N- (CH ₃ ) ₃ CL ⁶

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2 0 ^f J b »'/ ι r /

CH ₂ -NC-CH ₂ Cl. C /

H, C

CH ₂ -NH-C-CH ₂ Cl

^C1 x

O Il

CH ₂ -NH-C-CH ₂ Cl

An isomer mixture of the compounds with χ = 1 and χ = 2 in a ratio of about 1: 1

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Λ \

Example 1: Stunted growth in grass (Festuca pratensis)

Solvent: methanol

Emulsifier: polyethylene sorbitan monolaurate

Mixed to produce an appropriate preparation of active ingredients 1 part by weight of active ingredient with the stated amounts of solvent and emulsifier and filled with water on the desired focus on.

Grass plants 3 to 4 cm high are sprayed to runoff with the active compound preparations. After 14 days, the increment is measured and the inhibition of growth is calculated as a percentage of the increment in the control plants. The claims are classified with the numbers 0 to 5, where "0" ^and no damage "means and" 5 "" death of the plants. "

Active ingredients, active ingredient concentrations and results run out Table 1 below.

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Table 1

Grass growth lunatic (Festuca pratensis)

Active ingredient Conc entratlon inhibition damage in ppm 96 1 (known) 1000 _ 5 2 (known) 1000 60 2. 3 , 1000 75 2 4th 1000 80 0 5 1000 40 0 6th 1000 75 0 7th 1000 60 0 8th 1000 60 0

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Example 2; Growth retardation in grass (Lolium perenne)

Solvent: methanol

Emulsifier: polyethylene sorbitan monolaurate

Mixed to produce an appropriate preparation of active ingredients 1 part by weight of active ingredient with the stated amounts of solvent and emulsifier and filled with water on the desired concentration on .. "

Grass plants 3 to 4 cm high are sprayed to runoff with the active compound preparations. After 14 days, the increment is measured and the inhibition of growth is calculated as a percentage of the increment in the control plants. The damage is classified with the numbers 0 to 5, where ¹¹ O "means" no damage "and" 5 "means" plant death ".

Active ingredients, active ingredient concentrations and results run out Table 2 below.

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Table 2

Growth retardation in grass (Lolium perenne)

Active ingredient - concentration inhibition damage 1 (known) in ppm % 2 (known) 1000 _ 5 3 1000 35 3 4th 1000 85 2 6th 1000 60 0 7 ' 1000 75 0 8th 1000 75 0 1000 70 0

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Example 5:
Inhibition of growth in barley

Solvent: 10 parts by weight of methanol emulsifier! 2 parts by weight of folyethylene sorbitan mono-

laurat

Mixed to produce an appropriate preparation of active ingredients 1 part by weight of active ingredient with the stated amounts of solvent and emulsifier and filled with water on the desired focus on.

Young barley plants 5 to 8 cm high are sprayed to runoff with the active ingredient preparation. After 14 days, the increment is measured and the inhibition of growth is calculated as a % of the increment of the control plants.

Active ingredient, active ingredient concentrations and results go from Table 3 below.

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Table 3

Inhibition of growth in barley

Active ingredient concentration inhibition damage in ppm % 9 (known) 1000 15th 0 3 1000 75 1 4th 1000 20th 0 5 1000 40 0 6th 1000 60 0 7th 1000 85 0 10 1000 20th 0 11 1000 25th 0

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4;

Inhibition of growth in wheat

Solventί 10 parts by weight of methanol Emulsifier ϊ 2 parts by weight polyethylene sorbitan mono

laurat

Mixed to produce an appropriate preparation of active ingredients to get 1 part by weight of active ingredient with the specified men-. gen solvent and emulsifier and fill with water on the ™ desired focus on.

Young, 5 to 8 cm high wheat plants are sprayed dripping wet with the active ingredient preparation. After 14 days, the increment is measured and the inhibition of growth is calculated as a % of the increment of the control plants.

Active ingredients, active ingredient concentration and results run out Table 4 below.

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Table 4

Growth growth in wheat

Active ingredient concentration inhibition damage in ppm % 9 (known) 1000 25th 0 3 1000 65 1 7th 1000 40 0 11 1000 50 0

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: 2 0 9 8 8 4/1 3 7 p

Example 5: Growth inhibition "in maize

Solvent: 10 parts by weight of methanol

Emulsifier: 2 parts by weight of polyethylene sorbitan mono-

laurat

Mixed to produce an appropriate preparation of active ingredients 1 part by weight of active ingredient with the stated amounts of solvent and emulsifier and filled with water on the desired focus on.

Young maize plants 10-12 cm high are sprayed drop-wet with the preparation of the active compound. After 14 days, the growth is measured and the inhibition of growth in% of the growth of the
Control plants.

Active ingredients, active ingredient concentration and results run out
Table 5 below.

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Table 5

Inhibition of growth in maize

Active ingredient concentration inhibition damage in ppm % 9 (known) 1000 15th 0 3 1,000 60 0 5 1000 60 2 10 1000 45 0 11 1000 30th 1 12th 1000 80 0

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Manufacturing example:

To a solution of 22.5 g (0.2 mol) of chloroacetyl chloride in 100 ml of dry acetone are added dropwise at 5-10 ° a mixture of 22.6 g (0.2 mol) of 2,3-dihydro-pyranyl- (2) -methylamine and 20.2 g (0.2 mol) of triethylamine. The mixture is stirred for 1 hour at room temperature, poured into 500 ml of water and extracted twice with 200 ml of benzene each time. The over sodium sulfate dried benzene solution is evaporated in vacuo, the residue is distilled.

Kp _{0 2:} 128-130 ° C; F: 56 - 58 ° C i

Yield: 25 g (66 % of theory)

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Claims (9)

Patent claims: 1.) Growth-suppressing agents, characterized by a Content of chloroacetic acid amides saturated or unsaturated in the ring system the formula R 0 ■ CH ₂ -NC-CH ₂ Cl in which X is a CH ₂ group or an oxygen atom, R is a hydrogen atom, an alkyl, alkenyl or Alkynyl group with 1-6 carbon atoms, R, R and R ^ hydrogen, lower alkyl groups, optionally substituted aralkyl groups or optionally substituted rtuuted aryl groups and η Ο or 1 means. 2.) A method for dampening the growth of grass-like (monocotyledonous) plants, characterized in that chloroacetic acid amides of the formula I according to claim 1 is used. 3.) The method according to claim 2, characterized in that the active ingredient used is chloroacetic acid-furfuryl- (2) -amide. 4.) Process according to claim 2, characterized in that the active ingredient is chloroacetic acid tetrahydrofurfuryl (2) amide used. 5.) The method according to claim 2, characterized in that the active ingredient is chloroacetic acid - ^, 3-dihydro-pyranyl- (2) -methylf-amide used. Le A 13 869 - 22 - 209884/1376 6.) Method according to claim 2, characterized in that the active ingredient is chiloroacetic acid-jEetrahydro-pyranyl- (2) -methyl] -amide used. hy) chloroacetic acid {2,3-dihydro-pyranyl- (2 J-methyl] -amide. 8.) Use of chloroacetic acid amides of the formula I according to claim 1 for dampening plant growth. 9.) Process for the preparation of growth suppressants, characterized in that the chloroacetic acid amides Formula I according to claim 1 with extenders and / or surface-active Means mixed up. Le A 13 869 - 23 - 209884 / 137b