DE2343362A1 - Ethylene-precursor plant growth regulants - contg. propionaldehyde or alpha-keto-valeric acid derivs. - Google Patents

Abstract

Plant reactions are produced by applying to a plant a cpd. of formula CH3-CH2-X-CY-Z (I) (where Y is O or S; X is -CRR1-,O or S; R and R1 are H, alkyl or alkoxyalkyl or when Y is O, alkylene substd. by phenyl, 1-5C alkoxyphenyl, 1-5C alkylphenyl, halophenyl, alkoxycarbonyl, phenylthioalkyl, alkylthioalkyl, benzyl, substd. benzyl, hydroxybenzyl or halobenzyl; and Z is H, carboxy, carboxy salt, 1-6C alkyxycarbonyl, carboxamido, alkyl, alkoxy, 1-5C alkylthio, carboxyalkyl, carboxyalkoxy, alkylsulphonyl, alkoxycarbonyloxy, or phenyl opt. substd. by halogen, 1-5C alkyl, OH, 1-5C alkoxy, 2-5C alkenyl, 2-5C alkanoyloxy, CF3, CN, NO2, alkylthiophenyl, aminoalkyl, monoalkylaminoalkyl or dialkylaminoalkyl) or enol alkanoates of (I; X = CH2, Y = O, Z = COOH). New compsns. contain (I) or enol alkanoates of (I; X = CH2, Y = O, Z = COOH), a quencher, a light absorber of reflector, and a carrier. After application to plants, (I) undergo photolysis to release ethylene, which has plant-growth regulating and herbicidal props. The release of ethylene can be extended over relatively prolonged periods, and is accompanied by the formation of non-toxic degradation prods.

Description

The invention relates to the production of ethylene for use as a bioregulant or herbicide.

In particular, the invention relates to the photolytic degradation of propyl ketone or ethyl ester compounds with production of ethylene for use as a bioregulant or herbicide.

The photolytic degradation process with the production of ethylene can be carried out on the basis of the conversion of 2-oxovaleric acid the following reaction equation can be illustrated:

subsequently changed

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OO 0 0

CH ₃ CH ₂ CH ₂ CCO H -ili, CH ₂ = CH ₂ + CH ₃ CCOH

It is known that ethylene causes many plant reactions, including the elimination of apical dominance, stimulation of lateral or basal growth of buds, Control of vegetative growth, lot + -. Separation of leaves, flowers and fruits, control of formation of flowers, fruits and the ripening of fruits, induction of root formation, plant vigor or steepness, Modification of geotropic reactions, induction of chlorophyll decomposition, control of enzyme system induction, Metabolism, respiration, seed germination, auxin transport, Cell shape, stimulation of dormat plant tissue, modification of flower sex and stimulation of latex flow.

It is also known that ethylene has herbicidal effects depending on the type of plant, the ethylene concentration, the duration of treatment and many other factors.

The object of the invention is therefore to find a means that can be applied to plants so that it has sufficient time to undergo the above-mentioned plant reactions cause ethylene to be set free.

Another object of the invention is to find ethylene generating agents that are relatively cheap and are readily available.

Another object of the invention is to find ethylene generants which are non-toxic degradation products form.

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These objects are achieved according to the invention by the photolytic breakdown of a compound of the formula:

Y
CH ₃ -CH ₂ -XCZ

in which Y can be oxygen or sulfur and

/ ^R
is preferably oxygen, X can be C-, O or S.

/ ^{R 1}

and is preferably -C-, or 0 (in which Y is S), and

¹ / ^R
in particular X is -C-, wherein each R and R *

Hydrogen, alkyl (preferably C, g-alkyl) or alkoxyalkyl (preferably alkoxyalkyl with up to six carbon atoms) and, if Y is 0, X can also be substituted all-ylene, v; whether the substituent is phenyl, C- i_c -alkoxyphonyl, C ₁ r-alkylphenyl, halophenyl, alkoxycarbonyl (preferably alkoxycarbonyl with up to four carbon atoms), phenylthioalkyl (preferably phenylthio-C _? -alkyl), 7vlkylthioalkyl (preferably alkylthioalkyl with up to six carbon atoms); Benzyl, substituted benzyl, such as C, _r -alkoxybenzyl, hydroxybenzyl or halobenzyl can be; and Z is hydrogen, carboxy and carboxy salts, such as amine salts, / irnionium salts, alkali and alkaline earth salts, C, ..- alkoxycarbonyl, carboxamido, alkyl (preferably C4 ...- alkyl and especially C _{1 C} -alkyl), alkoxy (preferably C, ^ -alkoxy), C, _r -alkylthio, carboxyalkyl (preferably carboxy-C, ₃ -alkyl), carboxyalkoxy (preferably _{carboxy-C, 3} -alkoxy), alkylsulfonyl (preferably C,, - alkylsulfonyl), alkoxycarbonyloxy (preferably C ._, - alkoxycarbonyloxy), phenyl, substituted phenyl, in which the substituent is halogen, C, - alkyl,

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Hydroxy, C 1, - alkoxy, C ₂ _, - alkenyl, C ₂ _j - alkanoyloxy, trifluoromethyl, cyano, nitro, alkylthiophenyl (preferably C, ₅ -alkylthiophenyl), aminoalkyl (preferably C., (- aminoalkyl ), monoalkylaminoalkyl (preferably mono-c._ ₃ ~ alkyIaInInO-C ₁ _.- alkyl) or dialkylaminoalkyl (preferably C _1, dialkylamino-C, "alkyl) or an enol-C ₂ _c-alkanoate, such as acetate , propionate or butyrate

can, if X -C- in which at least one of the radicals

^No. i

R and R _{1 is} hydrogen, Y is oxygen and Z is carboxy.

Preferably, the compounds used according to the invention are those in which each R and R ₁ is hydrogen or Cj_ ₆ alkyl, such as methyl, ethyl, propyl, isopropyl or butyl, and especially those in which R is hydrogen and R ₁ is hydrogen, C., - is alkyl; Y is oxygen and Z is carboxy, carboxy salts, such as ammonium, alkali or alkaline earth salts (Na, K, Li), Cg-alkoxycarbonyl, carboxainido, phenyl, C, ₅ -alkylphenyl (such as p-butylphenyl or m-methylphenyl), C ._ ₅ -alkoxyphenyl (such as o- or p-methoxyphenyl, or m-ethoxyphenyl), nitrophenyl, cyanophenyl, C ₂ __- alkanoyloxyphenyl (acetyloxyphenyl or propionyloxyphenyl) or CF., - phenyl or C, (.-Alkoxy.

The most preferred compounds according to the invention are those in which X is methylene, Y is oxygen and Z is carboxy, carboxainido, C, ₅ ~ alkoxycarbonyl (such as methoxy, propoxy or butoxycarbonyl), CF - phenyl or an alkali or Alkaline earth carboxy salt (such as Na, K, Li) is.

The compounds according to the invention can be applied to plants by preparing a composition

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which is about 10 to 97% on an inert carrier, about 0.05 to 45% by weight, preferably 1 to 20% and in particular Contains 2 to 15% of the active ingredient and about 1 to 45% of auxiliary materials. As a carrier is a solvent or Dry-bulking agent meant. These compositions can therefore contain solids, such as dust, Granules or wettable powders, or they can be liquids, such as solutions, emulsions, suspensions and liquids Aerosols. Dusts can be produced by mixing the active ingredient with a solid inert carrier, such as Talc, clay, silica, pyrophylite, and the like, ground and mixed. Granules can be produced by using granular carriers such as attapulgites or vermiculites, usually with a particle size in the Range of about 0.05 to 1.5 mm, with the active ingredient, usually in a suitable solvent, for example water, dispersed or dissolved, impregnated or a coated inert carrier with a wettable powder containing the compound. If the active ingredient is crystalline Material, it is usually finely ground so that the finished product is easily removed from the atomizer flows out and spreads out easily. The active ingredient lies in dusts obtained with liquid active ingredients concentration usually between 1 and 2o% and especially 2 to 5%. For the preparation of solutions you can the active ingredients in a suitable non-volatile, non-phytotoxic solvent such as a petroleum distillate, a mineral or vegetable oil, for example crude or refined kerosene, cottonseed oil, Linseed oil, palm oil or another suitable solvent can be dissolved. The active ingredient can also be used with aids, such as humectants, penetrants, adhesives and / or other auxiliaries, used together will. Suitable humectants are polyvalent Al

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• α.

alcohols such as glycerin and glycols. Suitable penetrants and adhesion improvers are Dt-1-p-menthene, drying oils, such as, for example, unsaturated fatty acid esters of glycerine, trimethylnonanol / ethylene oxide complex, alkylaryl polyoxyethylene glycols, mixed petroleum distillates, alkylsulphates, diethylene glycols, abietate, alkylaminoacetates, alkylsopropyl alcohols, diethyleneglycol, abietate, alkylaminoacetates, alkylaminoacetates, isopropyl alcohols and glycols, alkylaryl polyoxyethylene ethers and glycols, and Triton-D-19 56, a modified alkylated phthalic acid / glycerin resin. However, the preferred carrier for the active ingredients is water. Some of the active ingredients according to the invention are sufficiently soluble in water to be able to be used directly in this solvent. However, some of the active ingredients are not sufficiently soluble in water and must be made soluble. Those active ingredients which have an acidic or basic function can be made soluble by converting them into their salts, such as amine or mineral acid salts. Alternatively, these compounds can be solubilized by using a water-miscible organic solvent, such as an alcohol or a ketone, in addition to water.

Surface-active agents can be incorporated into liquid agents according to the invention in order to improve the spreadability of the agent on plant surfaces and to facilitate the penetration of the active compounds into the plant tissue. These surfactants can be anionic, cationic or nonionic. Examples of suitable anionic surface-active agents are soaps and sodium salts of long-chain alkyl sulfates, alkyl naphthalene sulfonates or alkyl sulfosuccinates. Examples of suitable cationic surfactants are long chain alkyl dibenzyl ammonium chlorides or alkyl pyridinium salts and cetyl pyridinium chloride.

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In order to prevent Teilfotolyse or complete photolysis of the compounds according to the invention, before they have penetrated the plant tissue are agents that energy quencher (quenching agent) contained used. When using the enol alkanoates, however, such a quencher or some other means which absorbs or reflects light is not necessary. Suitable extinguishers or triplet energy acceptors are .1,3- cyclohexadiene, myrcene and vegetable oils that contain unsaturated compounds, lipids or terpenes such as linseed oil or turpentine. UV absorbers such as 2-hydroxybenzophenones and 2- (hydroxyphenyl) -benzotriazoles are also suitable. The amount of extinguisher used depends on its effectiveness. Such an extinguisher is expediently used in molar concentrations of 10 to 100%, in particular 40 to 100% of the molar concentration of the ethylene generator.

Instead of the extinguishers, means that reflect or absorb light can be used, since this too is premature Prevent decomposition of the ethylene generator. White inorganic compounds, such as titanium dioxide, potassium carbonate and magnesium phosphate are used, while carbon black and for light absorption Activated charcoal are suitable and used in the same proportions as the extinguisher.

For practical use as a plant growth regulator the compounds according to the invention are therefore generally in compositions that have a inert carrier and a quencher containing an absorbent and / or reflective agent, introduced.

When the ethylene generating agent is applied to the plant, a photolytic one occurs when exposed to light Dismantling. This degradation, which occurs on the plant surface

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surface or within the plant when the ethylene generating agent is rapidly absorbed by the plant, can use, leads to the formation of ethylene. The ethylene that is formed during the aforementioned photolytic degradation produces the desired bio-regulating or herbicidal effect as described above.

The following examples illustrate the invention.

example 1

This example illustrates the photolytic degradation of 2-oxovaleric acid with the formation of ethylene Laboratory conditions.

A solution of 1 g of 2-oxovaleric acid in 150 ml of benzene is placed in a quartz container. The container is flushed with nitrogen and 11 hours with UV light (2537 A) irradiated. During the irradiation, nitrogen is passed through the reaction solution and from there into a Row of chilled reaction tubes containing bromine in carbon tetrachloride included, led. A dry ice trap is used to separate entrained benzene. After the end of the irradiation, the solutions in the test tubes are combined and distilled concentrated by a Vigreaux column to separate material boiling at 76 to 78 ° C. You get 1.49 g residue. The NMR spectrum of the residue is the same as that of authentic ethylene dibromide.

The identity is further determined by comparing the above Residue with the residue obtained by equal evaporation of a mixture of authentic ethylene dibromide, Bromine and carbon tetrachloride is obtained. The IR spectra of both residues are identical.

14 389 IB Q

When residue samples are passed through an SE30 column in an aerograph gas chromatograph at 55, show the plots have the same migration speeds (retention times) and curves have the same shape.

The formation of ethylene during photolysis is caused by isolation of the dibromide derivative shown.

Example 2

This example illustrates the growth-inhibiting and herbicidal effect of 2-oxovaleric acid _# especially when used as a pre-emergence herbicide or on young plants.

Styrofoam shells are up to 1.3 cm (one half inch) from the upper end filled with sand. Then a thin layer of fine sand is placed on top as a seed bed. Seeds of Short life-cycle strains of Trifolium variegatum, Senecio vulgare, Schism arabicus and Plantago insularis are in the fine sand introduced, watered with nutrient solution and with the testcheiTiischem sprayed in an amount of 5 and 50 ppm based on the weight of the sand. Other cultures v / earth retained for post-emergence tests. When the plants are Io and 2o days old, they become 5 and 50 ppm of the chemicals sprayed. The results are summarized below:

- Q _

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40.

Compound ppm Trifolium Senecio Schism Plantago 2-oxovaleric acid

Pre-emergence: '5 D. LC D. D. 5o D. LC D. D. Post-emergence: 5 SD SD SD SD 10 days 5o SD SD SD SD Post-emergence: 5 N R. R. N 2o days 5o N R. R. N

Abbreviations:

D = dead

LC = sheet curling
S = stunted growth R = retarded
N = normal

Example 3

This example illustrates the effect of ethylene on the yield of latex from rubber trees.

Agents containing 2-0xovaleric acid were applied to the scratched bark of rubber trees under the tap upset. Sixteen trees were used per treatment. The trees were "clone Thir 1". The table below shows the mean yields in grams of dry rubber each Tree per tap, taking into account differences in pre-treatment for the first seven weeks after application compiled:

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Compound yield percentage

yield

Palm oil alone 62.9 loo

5% 2-oxovaleric acid in palm oil 12o, 4

1o% 2-oxovaleric acid in palm oil 1o8.4

15% 2-oxovaleric acid in palm oil 119.6

Example 4

1o g 2-oxovaleric acid, 2o g Emerest 2652 (polyethylene glycol dilaurate) and 2o g Galfac PE-51o (acid phosphoric acid alkyl ester) v / earth dissolved in 50 g cottonseed oil. The agent obtained can be applied to plants in order to bring about the desired reaction.

Example 5

1 g of 1,3-hexadiene is dissolved in 10 g of 2-oxovaleric acid. The solution obtained is dissolved in 80 g of palm oil. This agent can be applied to plants to the desired Induce reaction.

Example 6

2.5 g of 1,3-cyclohexadiene are dissolved in 15 g of 2-oxovaleric acid solved. The solution obtained is dissolved in 100 g of linseed oil. This remedy can be sprayed on to plants bring about the desired reaction.

Example 7

1 g of titanium dioxide is suspended in 12 g of 2-acetoxy-2-pentenoic acid. The resulting mixture is mixed with 75 g of linseed oil

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diluted. This agent can be applied to plants to induce the desired response.

Example 8

g of carbon black is suspended in 12 g of 2-acetoxy-2-pentenoic acid. The mixture obtained is diluted with 75 g of cottonseed oil. This agent can be applied to plants to induce the desired response.

If instead of the 2-acetoxy-2-pentenoic acid used in Example 7

Phenylpropyl ketone, (2-methylphenyl) propyl ketone, (2,5-dimethylphenyl) propyl ketone, (2-methoxyphenyl) propyl ketone, (4-butylphenyl) propyl ketone, (2-acetyloxyphenyl) propyl ketone, (3-trifluoromethylphenyl) propyl ketone, dipropyl ketone,
(2-Nitrophenyl) propyl ketone, (2-cyanophenyl) propyl ketone, 2-butyl methyl ketone, 1-methoxypropylphenyl ketone, methyl 2-oxovalerate, sodium 2-oxovalerate, 2-oxovaleramide, or (1-phenylpropyl) methyl ketone

are used, the same results are obtained.

If instead of the 2-0xovaleric acid used in Example 6

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Phenylpropyl ketone, (2-MethyIpheny1) -propylketone, (2 _f 5-Dimethylphenyl) -propylketone, (2-Methoxyphenyl) -propylketon, (4-ButyIpheny1) -propylketon, (2-Acetyloxyphenyl) -propylphenketone, (3- propyl ketone, dipropyl ketone,
(2-Nitrophenyl) propyl ketone, (2-cyanophenyl) propyl ketone, 2-butyl methyl ketone, 1-methoxypropyl phenyl ketone, methyl 2-oxovalerate, sodium 2-oxovalerate, 2-oxovaleramide, or (1-phenylpropyl) methyl ketone

uses v / earth, so v / earth achieves the same results,

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Claims (15)

14 389 IB ^ Z 34 O 3b Claims Process for generating plant reactions, characterized in that one on a plant a compound of the formula Il CH ₃ -CH ₂ XCZ in which Y can be oxygen or sulfur, X -C-, 0 or S, wherein each R and R is hydrogen, alkyl or alkoxyalkyl, and when Y is 0, X is also substituted alkylene, wherein the substituent is phenyl, C, ₅ ~ alkoxyphenyl, c._ ₅ alkylphenyl, halophenyl, alkoxycarbonyl , Phenylthioalkyl, alkylthioalkyl, benzyl, substituted benzyl, hydroxybenzyl or halobenzyl can be; and Z is hydrogen, carboxy and carboxy salts, C ._ ^ - alkoxycarbonyl, carboxamido, alkyl, alkoxy, C. --Alky1-thio, carboxyalkyl, carboxyalkoxy, alky! sulfonyl, alkoxycarbonyloxy, phenyl, substituted phenyl, in which the substituent is halogen, ' C, C-alkyl, hydroxy, C, ^ alkoxy, C ₂ _ ₅ alkenyl, C ₂ _ ₅ alkanoyloxy, trifluoromethyl, cyano, nitro, alkylthiophenyl, aminoalkyl, monoalkylaminoalkyl or dialkylaminoalkyl may be, can be; or the enol alkanoate thereof when X is methylene, Y is oxygen and Z is carboxy. 2) The method according to claim 1, characterized ,, that X -C-, wherein each of the radicals ^N R - 14 - 509811/1171 14 389 IB R and R _{1 is} hydrogen or C ₁ / alkyl; Y Sauer-I ι - o fabric is; and Z is carboxy, carboxy salts, C 1, -alkoxycarbonyl, carboxamido, phenyl, C, ς-alky! phenyl, ^c i_5 -alkoxyphenyl, nitrophenyl, cyanophenyl, Cj ^ -alkanoyloxyphenyl, CF -phenyl or C 1, -alkoxy. 3) Method according to claim 1, characterized that X is methylene, Y is oxygen and Z is carboxy, carboxamido, C., [- alkoxy carbonyl, CF., - phenyl or an alkali or alkaline earth carboxy salt. 4) Method according spoke 1, characterized in that the compound 2-oxovaleric acid is. 5) Method according to claim 1, characterized in that that the compound is 2-acetoxy-2-pentenoic acid. 6) Composition of the substance, indicated by it, that they are about 0.5 to 45 wt. ΐ of a compound of the formula Il CH ₃ -CH ₂ -XCZ in which Y can be oxygen or sulfur, X -C- , Can be 0 or S, where each of the radicals R and R .. hydrogen, Is alkyl or alkoxyalkyl, and when Y is 0, X is also substituted alkylene in which the substituent. Phenyl, C ^ -alkoxyphenyl, C ^ -alkylphenyl, halophenyl, Alkoxycarbonyl, phenylthioalkyl, alkylthioalkyl, - 15 - 509811/1171 Benzyl, substituted benzyl, hydroxybenzyl or halobenzyl can be; and Z hydrogen,
Carboxy and carboxy salts, C, g-alkoxycarbonyl, carboxamido, alkyl, alkoxy, C, ₅ -alkylthio, carboxyalkyl, carboxyalkoxy, alkylsulfonyl, alkoxycarbonyloxy,
Phenyl, substituted phenyl, in which the substituent is halogen, C ₁ -C -alkyl, hydroxy, C, 5-alkoxy, C 2-5 -alkenyl, C ₂ -C -alkanoyloxy, trifluoromethyl, cyano, nitro, alkylthio, phenyl, aminoalkyl, monoalkylaminoalkyl or dialkylaminoalkyl can be; or their enol alkanoate when X is methylene, Y is oxygen and Z is carboxy; an energy extinguisher (quencher), light absorber or light reflector; and includes a carrier. 7) substance composition according to claim 6, characterized marked that X -C-, in which each of the radicals R and R _{1 is} hydrogen, ^ R ' or C 1-4 alkyl; Y is oxygen; and Z
Carboxy, carboxy salts, C -.- alkoxycarbonyl, carboxamido, phenyl, C, - alkylphenyl, C, c-alkoxyphenyl, nitrophenyl, cyanophenyl, C ₂ _ ₅ -Alkanoyloxyphenyl,
Is CF ₃ phenyl or C _1-5 alkoxy. 8) composition of matter according to claim 6, characterized in that X is methylene, Y
Oxygen and Z is carboxy, carboxamido, C ,, - alkoxy, CF ₃ ~ phenyl or an alkali or Erdalkalicarboxysalz is. 9) composition of matter according to claim 6, characterized in that the compound
Is 2-oxovaleric acid. - 16 - 509811/1171 10) composition of matter according to claim 6, characterized characterized in that the compound is 2-acetoxy-2-pentenoic acid. 11) composition of matter according to claim 6, characterized characterized in that the carrier is a non-volatile oil. 12) composition of matter according to claim 11, characterized characterized in that the oil is a vegetable oil. 13) composition of matter according to claim 11, characterized G. ekenn indicates that the oil is a mineral oil. 14) 'substance composition according to claim 6, characterized in that it is an energy extinguisher (quencher) contains. 15) composition of matter according to claim 6, characterized in that it is a light contains reflective material. - 17 - 509811/1171