CH666990A5 - METHOD FOR PRODUCING A PLANT TREATMENT PRODUCT. - Google Patents

Description

DESCRIPTION It has already been proposed to use certain crops, namely cotton plants (Gossypium)

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Treat growth control with 2-chloroethylphosphonic acid (hereinafter also called ethephon for short), especially with regard to defoliation before the capsules are harvested.

It has been found that new and improved plant treatment compositions according to the invention are obtained by a process having the features mentioned in claim 1. The plant treatment agents obtained by the process according to the invention can (I) mixtures of the compounds (a) and (b) used in the process according to the invention, or (II) complex compounds of the compounds (a) and (b), or (III) mixtures of complex compounds (II ) with the uncomplexed compounds (a). (b) be or contain. In general, the stability of many complex compounds (II) is low in the presence of moisture, so that the presence of water leads to the decomposition of the complexes (II) into the compounds (a) and (b) or prevents the formation of the complexes (II) can.

Preferred embodiments of the method have the features specified in claims 2 to 7.

The invention further relates, according to claim 8, to the plant treatment composition obtained by the process, of which embodiments are described in claims 9 to 11, and to a method for regulating plant growth with the features specified in claim 12, of which claims 13 to 15 define embodiments .

H-

The agents obtainable by the method according to the invention are generally useful for regulating plant growth and can promote or inhibit growth as well as ripening, which can be influenced by the concentration of the agent.

The growth-promoting effects include early breaking of the buds, synchronization of fruit ripening and falling of the leaves, temporarily increasing the flow of tree sap or latex, interrupting the dormancy of treated seeds, onions and tubers. Inhibitory effects are e.g. Leaf waste, stunted growth and regulation of top dominance. The agents are particularly effective in the treatment of tobacco plants, cotton plants, wheat, vegetables, fruits and rubber trees.

In formulas (1) and (10), R is a divalent alkane radical having 1 to 6, preferably 1 to 4 and in particular 1 to 2 carbon atoms; X represents halogen, e.g. Fluorine, chlorine, bromine or iodine; the optionally formed N-heterocyclic ring may contain 3 to 5 carbon atoms and may be saturated or unsaturated.

When compounds (b) are used in the form of polymers with repeating units of the formula (40), the compounds (a) can be used to obtain polymers which can be assigned the following structure (41):

Oh

-ch-

(41)

where n is a number from 1 to 5000 and the structure can additionally contain repeating units of an unsubstituted N-vinylheterocyclic ring and / or units of a derivative of the above dimers which is monosubstituted with the haloalkyldihydro-xyphosphoryl group.

Agents obtained according to the invention, regardless of whether they contain the compounds (a) and (b) in complexed or non-complexed form, can be used directly for the treatment of plants. For economic reasons and because of the better distribution, they are preferably mixed with an inert diluent or carrier material, which is preferably a liquid, such as e.g. Water. Xylene, toluene. Cyclohexane or paraffins, mineral oil fractions, other inert organic liquids or mixtures as are customary as inert carriers. The concentration of (b) in the spray solution can e.g. vary between about 150 bpm and about 12,000 bpm, preferably between about 300 bpm and about 10,000 bpm. The liquid carrier can include surfactants such as. B. polyoxyalkylene fatty acid ester or alcohol ether, lignin, methyl cellulose, etc. .. contain. Water can also be used together with the organic solvents mentioned.

The plant treatment agent can also be a paste. be a powder or granules, with extenders such as talc, bentonite, clays, diatomaceous earth, kaolins and other conventional solid extenders used in the same proportions as the liquid carriers, and e.g. B. can be applied to the plants by spraying or dusting.

Among the complex compounds obtainable according to the invention, preference is given to those which are formed from cyclic amides as compounds (b), in particular the complexes from 2-haloethylphosphonic acid and N-methyl-2-pyrrolidone.

However, plant treatment agents in the form of non-complexed mixtures 60 of N-methyl-2-pyrrolidone and β-haloethylphosphonic acid are also according to the invention. preferably ß-chloroethylphosphonic acid, available, these compounds preferably in (a) :( b) fractions from 1: 0.05 to 1: 4, in particular in (a): (b) fractions from 1: 0.1 to 1: 3, can be used.

65 The dosage of the agent in the treatment of plants can be adapted to the respective requirements. For example, that from ß-haloethylphosphonic acid as compound (a) and N-methyl-2-pyrrolidone as compound

(b) agents obtained when applied to cotton plants before harvest and after capsule formation in doses between about 0.0015 and about 0.125 g of compound (b) per plant, preferably between about 0.003 and about 0.095 g of compound (b) per plant; Treatment agents containing carriers are typically used in amounts between about 0.1 and about 100 kg per hectare, preferably between about 1 and about 10 kg per hectare.

When applied to cotton, it is also advisable to apply the treatment agent at least 30 days after the formation of the protective sheet; it can be used practically until the capsules are broken open for the first time without harm to the plant or plant fiber, and thereby produce advantageous results.

The process according to the invention can generally be carried out by compound (a) and compound (b) in a reactor in molar ratios between about 0.2: 1 and about 4: 1, preferably about 1: 1 and about 3: 1 brings together, if desired in the presence of solvents such as. B. ether, ketone, optionally chlorinated liquid hydrocarbons, O-heterocyclic compound, water or other inert liquid solvents or dispersants. Suitable solvents are e.g. Methyl ethyl ether, diethyl ether, methyl ethyl ketone, diethyl ketone, chloroform, carbon tetrachloride, benzene, toluene, xylene, tetrahydrofuran, furfural, cyclohexane, hexane, heptane, octane etc.

The process is preferably carried out in the presence of water or a solvent in which the product is insoluble. Despite the dissociation of complexes obtainable according to the invention, especially if they are present in dilutions of less than 2 mol of complex to 3 mol of water, the complex is regressed when the water evaporates.

The process can thus be carried out under anhydrous or non-anhydrous conditions, preferably with stirring, and is usually completed within a period of at most 2 hours.

According to a preferred form of the process, the compounds (a) and (b) are dissolved or suspended in concentrations of between 20 and 60% by weight in the chosen solvent.

The formation of homogeneous products can be indicated by the removal of a lower oily phase if the product is insoluble in the solvent; the top layer can then be stripped off and the oily phase recovered as the product. The solvent can also be removed by evaporation, stripping, extraction, etc. On the other hand, the product can be obtained as a solution and applied in this form.

The addition of carriers, e.g. Emulsions or solutions, which may contain mineral or vegetable oils, or water or aqueous solutions of organic solvents can be carried out in the usual way. The concentration of the agents obtained according to the invention in the carrier is typically between approximately 15 ppm and approximately 150,000 ppm, preferably between approximately 25 ppm and approximately 100,000 ppm. Such agents can be used in dosages between about 0.1 and about 100 kg / ha, preferably between about 0.5 and about 50 kg / ha.

The agents obtained according to the invention can be applied to the plants as particulate solids or as a liquid. For use as a liquid, the agent can be formed as a prepared solution on the plants or plant site, e.g. by using a solution of haloethylphosphonic acid (a) and a solution of compound (b) as a separate spray solution.

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Of course, the agent or treatment solution can contain surfactants, thickeners and / or other agricultural chemicals such as e.g. Algicides, fungicides, herbicides, insecticides, nematocides, disinfectants or other plant treatment compositions or mixtures thereof, provided the activity of the compositions obtained according to the invention is not reduced. Examples of additives that can be used with agents obtained according to the invention are the following:

Tributylphosphorus trithioate or itite (DEF or FO-LEX); l, l-dimethyl-4,4'-bipyrridinium salts, e.g. the methyl sulfate salt or halogenite salt (paraquat); Sodium chlorate; an alkali metal salt of cacodylic acid, e.g. the sodium salt "BOLL's-EYE"; chlorinated isophthalenitriles, e.g. the tetrachlorinated derivative daconil; Alkyl l- (butylcarbamoyl) -2-benzimidazole carbamate, e.g. the methyl derivative Be-nomyl; Dialkylaminobenzene diazoalkali sulfates, e.g. the di-methyid derivative Dexon; 2,4-dinitro-6-alkylphenyl crotonate, e.g. the octyl derivative Karathan; Manganese ethyl bis (dithiocarbamate) e.g. Maneb or Manzat; 2,3-dihydro-5-carboanido-6-methyl-l, 4-oxathiin-4,4-dioxide (Plantvax); Polychloro nitrobenzenes, e.g. the pentachlor derivative Terraclor; 5-ethoxy-3-thrichloromethyl-l, 2,4-thiadiazole terrazole; 5,6-dihydro

2-methyl-l, 4-oxathiin-3-carboxanilide Vitavax; Tetramethyl thiuram disulfide arasan; N- (acyl) tert-amidoalkyl) anilides such as lasso; Esters of cyclopropane-substituted carboxylic acids; Alkylsulfinyl substituted diphenyl ether; Alkyl 1,2-dimethyl-3,5-diphenylpyrazolium salts and derivatives thereof; Diethylamino-2,6-dinitro-4-trifluoromethylbenzene and derivatives such as the amino-substituted derivative Cobex; Dinitroaniline; Trifluoromethyl nitrodiphenyl ether; Halogen-N-cyclic-imidoalkylene-substituted acetanilides; Dichloro-nitrobenzoic acid and derivatives thereof, e.g. Dinobes; Phosphonium salts such as phosphon; halogenated benzoic acids such as 2,3,6-TBA or Benzac, 2,4-D and 2,4,5-T; Amino dihalobenzoic acids such as amiben; Polychlorophenyl nitro phenylate ether such as Modown; 6-benzylaminopurine (benzyl adenine); Arylazomalone nitriles; Dimethylformamide; Methyl acetamide; Dimethylacetamide; 2-propyl-2-chloroethyl-trifluoro-dinitropropyltoluidine (basalin); N, N-bis (phosphonomethyl) glycine (glyphosine); 5-chloro-3-methyl-4-nitro-1H-pyrazole; 2-chloroethyl trimethyl ammonium chloride (Cycocel or CCC); 2- (3-chlorophenoxy) propionic acid (3-CPA); 4-chlorophenoxyacetic acid (4-CPA); 3- (chlorophenyl) -1, l-dimethyl-urea (monuron); N-dodecylguanidine acetate (dodine); Urea; 2-haloethylphosphonic acid, e.g. Ethephon;

3-amino-1,2,4-triazole; Cycloheximide; 2- (3-chlorophenoxy) propionamide; Maleic hydrazide (1,2-di-hydropyridazine-3,6-dione); Ammonium thiocyanate; the alkali metal salt of 2,3-dichloro-l-methylpropionic acid (e.g. the sodium salt men-dok); 3- (3,4-dichlorophenyl) -1,1-dimethylurea (diuron); 6,7-dihydrodipyridopyrazidinium dibromide (Diquat); 2,4-dinitro-6-sec-butylphenol (dinoseb); N-2,4-dimethyl-5- (trifluoromethyl) sulfonylaminophenyl acetamide (mefluidide); Haloalkylsilane; 6-furfurylaminopurine (kinetin); 4-hydroxyethyl hydrazine (BOH); 1-hydroxytriacontane; 3-indole acetic acid (IAA); 3-indole butter acid (IBA); Abscisic acid (ABA); 1-naphthalene acetic acid (NAA); Dieldrin-hexa-chloro-epoxy-octahydro-endodimethane naphthalene (endrin); the 2,4-dichlorophenol ester of benzene (Genite);

N - [(tetrachloroethyl) thio] 4-cyclohexene-1,2-dicarboximide (difolatan 4F); Monosodium hydrogen methane arsonate (MSMA); Alkali metal salt of trichlorophenylacetic acid (Fenac); 2-naphthoxyacetic acid (BNOA); the alkylamine salt of succinic acid or 7-oxabicycloheptane-2,3-dicarboxylic acid (Endothall); Succinic acid-2,2-dimethyl-hydrazine (SADH or Alar); Giberellic acid (Activol or Gibrel); 2,3,5-triiodobenzoic acid (TIBA); Iron chelate; Sulfur; Ni

5

5

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30th

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60

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cotine sulfate; Lead resinate; self-emulsifying petroleum oil; Sodium selenate; Zinc ethylene bisdithio carbamate (Zineb); Tetramethyl thiuramide sulfide (THIRAM); N-trichloromethylthiotetrahydro-thalimide (Captan); Mercaptobenzolthio-zol (Rotax); l, l, l-trichloro-l, 2-bis (chlorophenyl) ethane (DDT) 2- (2,4,5-trichlorophenoxy) propionic acid (Silvex); 3,6-dichloro-o-anisic acid (Dicamba); 2,2-dichloropropionic acid (Dalapon); 2-chloro-4,6-bis (ethylamino) -S-triazine (Simazin); N, N-diallyl-2-chloroacetamide (CDAA); 2-chloroalkyl diethyl dithio carbamate (CDEC); Dimethyltetrachlorotaphthalate (DCPA or Dacthal); N-N-dimethyl-2,2-diphe-nylacetamide (diphenamide); Dimethyldithiocarbamate (Fer-bam or Ziram); Malathion; Actidion; Zinc dimethyldi-thiocarbamate (ziram); Hexahydromethanoindene (chlorodan); chlorinated dimethane naphthalene (dieldrin or Al-drin); Sodium N-methyldithiocarbamate dihydrate (Vapam); 2,2-dichlorovinyl dimethyl phosphate (Vapona or DDVP);

0- (2,4-dichlorophenyl) -0-methyl-isopropyl-phosphoramido-thiat (Zytron); Arsenic trioxide mixtures (sodite); Phosphomolybdic acid (PMA); 0,0-diethyl-0 (2-isopropyl-6-methyl-4-pyrimidinyl) phosphorothioate (diazinon); 1,1-bis (chlorophenyl) -2,2,2-trichloroethanol (Kelthane); 2,2-bis (p-methoxyphenyl) -l, l, l-trichloroethane (methoxychlor or DMDT); 2,4,4 ', 5-tetrachlorodiphenyl sulfone (Tedion); O —O-diethyl-0- (and S -) - 2- (ethylthio) ethyl-phosphorothioate (Sy-stox); Isopropyl-N- (3-chlorophenyl) carbamate (chlorine-IPC or CIPC); Sodium 2,4-dichlorophenoxyethyl sulfate (SES or Seson); Bordeaux mix; Preparations containing strepto-mycin (agrimycin); N-trichloromethylthiophthalimide (phaltan); Ethyl-mercury-II-chloride mixtures (Veresan); 3,5-dimethyl-2H-l, 3,5-tetrahydrothiadiazin-2-thione (Mylon); 1-naphthyl-N-methyl carbamate (carbaryl);

1-dimethyl-carbamoyl-5-methyl-3-pyrazolyl-dimethylcarbamate (dimethilane); 0,0-dimethyl-S- (N-methylcarbamoyl-methyl) phosphorodithioate (dimethoate); 3- (3,4-dichlorophenyl) -l-methoxy-l-methylurea (Linutron); 2-chloro-4,6-bis (ethylamino) -S-triazine (simazine); l, l, l-trifluoro-2,6-dinit-ro-N, N-dipropyl-p-toluidine (treflan or trifluralin); 4-dimethylamino-3,5-xylyl-N-methylcarbamate (Zectran); Iron III dimethyl dithiocarbamate (Ferbam); N-1-naphthyl phthalamic acid (NPA); S-propyl butyl ethyl thiocarbamate (PEBC); Disodium methane arsenate (sodar); Calcium hydrogen methyl arsinate (Calar); y-benzene hexachloride (lindane); Diethyl S-diethylaminoethyl phosphorothiolate (amiton or amitrole); Rotenon; Pyrethrum; the acaricide 2,4,5,4'-tetrachlorodiphenyl sulfone (Tedion) 1,1-dimethylpiperidinium salts, e.g. Metiguat chloride and Terpal; the anionic salts of allyltrimethylammonium, bromo-ethyltrimethylammonium, isopropyltrimethylammonium, N-chloroethyl-N, N-dimethylhydrazonium, N-bromoethyl-N, N-dimethylhydrazonium, N-isopropyl-N, N-dimethylhydrazonium, N-allyl-N, N-dimethylhydrazonium and

N - N-dimethylmorpholinium cations, as well as many other plant growth regulators and agricultural aids. Each of the aforementioned active auxiliaries is effective individually in amounts which depend on the specific substance, the particular intended use and the type of plants, the soil or other growth conditions. In general, these substances are used in amounts of between approximately 1 g / ha and approximately 44.8 kg / ha.

The same application amount can be used if such chemically active additives are applied separately. When used in a mixture, the known agents are preferably incorporated in amounts between about 0.01% and about 60% by weight based on the total weight of the composition. In general, it is preferred that the known agricultural aids are used in an amount that is within the empirical values for their respective application as the sole agent, although, because of the combination effect, smaller amounts within the range of the empirical values or amounts below are also suitable. Thus, amounts which are below the average of the empirical values generally give good results when they are combined with the agents prepared according to the invention, in particular from chloroethylphosphonic acid and N-methyl-2-pyrrolidone.

The new agents can be used on many plants, including gymnosperms and angiosperms of the monocotyledon and dicotyledon types. Types of these include vegetables, fruits, grasses, bushes, trees, ornamental plants and the like. Examples of living plants which can be treated alone or in mixtures with the agents obtained according to the invention include: fruit trees such as apple, peach, apricot, mandarin, pear, cherry, grapefruit, orange, lemon, lemon -, plum, plum, banana, gua-va, nectarine, olive, papaya, date, fig trees and their fruits and other trees such as: oak, hazelnut, beech, pecan, Almond, rubber, cork, pine, elm, spruce, fir, cedar, yew, eucalyptus, magnolia, dogwood, palm, walnut, willow, avocado, chestnut, hawthorn, maple, mango and the like. Examples of vegetables, which can be effectively treated with the agents or mixtures thereof according to the invention include: asparagus, beans, Brussels sprouts, carrots, cauliflower, celery, cucumber, pumpkin * ', lentils, lettuce, onions, peas, peanuts, pepper, potatoes, pumpkin " ', Soybeans, spinach, tomatoes, broccoli, cabbage, R practice and the like.

Examples of cereals and grasses which can be treated with the compositions or mixtures thereof obtained according to the invention include: barley, rye, oats, wheat, rice, corn, panicle grass etc.

Ornamental plants that can be treated effectively

are e.g. Rhododendron, roses, azaleas, tulips, carnations, chrysanthemums, dahlias, hyacinths, geraniums, balsam, iris, lilies, poinsettia, snapdragon, fuchsias, gladioli etc.

Other fruits which can be effectively treated with the agents or mixtures thereof obtained according to the invention include: pineapple, melons, grapes, hops, soft fruits such as cranberries, strawberries, raspberries, blueberries, blackberries and currants, coffee plants, sugar cane, flax, cotton, tobacco plants and the same.

As already stated, the agents produced according to the invention bring about the effects which are generally associated with the activity of ethylene, namely: regulation of peak dominance and promotion of branch formation, induction of bud formation and enlargement, induction of hardening, increased resistance to cold, coloring - and ripening, interruption of rest, reduction of stem (stem) elongation, increased flowering and fruit set, earlier harvest, resistance to change of location ("lodg-ing"), disease, waste of fruits and nuts, cracking open, promotion of Root formation and rhizome development, seed development, increased harvest yield and other effects.

For example, in the treatment of cotton plants, there is an increased yield in a single harvest as well as synchronization of capsule opening and leaf waste

+) Cucurbita maxima x) Cucurbita pepo

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20th

25th

30th

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50

55

60

65

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to effect the use of certain complexes, e.g. acid / N-methylpyrrolidone complexes (from about 1000 ppm to about 15,000 ppm in one carrier), preferably at least 30 days after the formation of the protective sheet. Details of the application have already been described above.

The agents obtained according to the invention are usually applied to the harvested area at a temperature which is as far as possible in the range from about 18 ° C. to 35 ° C. However, the use at higher or lower temperatures does not damage the harvest, but merely changes the time period in The period of time is extended at lower temperatures and shortened at higher temperatures. Normally, the effect appears within 5 to 14 days after the treatment, depending on the concentration of the active components and according to the existing temperature conditions the results were observed within 8 to 12 days in the case of low-dose use, and the results were found in the course of 5 to 7 days in the case of high-dose applications It was found that field temperatures of about 35 ° C. and more generally did not produce any dosage levels above 3000 TpM N- Methyl-2-pyrrolidone require, albeit high re dosage levels can be used without harm to plant or cotton fiber.

The advantages that can be achieved with such a treatment are listed below:

1. Creation of a multipurpose composition for capsule maturation, opening and leaf waste to avoid the need for multiple chemical applications.

2. Accelerate the opening of the capsules to produce more uniformly opened capsules when harvesting for the first time and synchronization of the defoliation process so that it occurs after the capsules are fully developed and open or open.

3. Synergistic interaction between the active ingredients of the composition to produce a metabolic effect of the increased opening of the capsules, which exceeds the sum of the effects that can be achieved with the individual components.

4. Accelerate the early opening of the capsules containing ripe fibers with no significant effect on the fully mature, breakaway capsules to increase the amount of cotton that can be brought in in a single first crop and reduce the need for a second crop and / or prevent.

5. Creation of high quality cotton fibers and, in certain cases, improvement of cotton fibers.

6. Reduction of the temperature sensitivity of the plant and resistance to breakup at low temperatures.

7. Allowing for later planting and / or 5 earlier harvesting.

8. Creation of economical and labor-saving harvesting of the cotton harvest.

The following examples serve to explain the invention in more detail. The stated amounts or proportions relate to the weight, unless otherwise noted.

Example I

The experiments described in Table I are comparative examples showing the opening of the capsules in percent, taking into account half-opened, open and ready-to-harvest capsules obtained from untreated plants (A), from plants treated with N-methylpyrrolidone. and ethephon compositions in various concentrations (B), 20 with a propylene glycol and ethephon composition (C), with N-pyrrolidone as the sole active ingredient (D) and with ethephon as the sole active ingredient (E) in aqueous solutions , received.

Each of the 4 groups (B-E) with five 12-week-old 25 Gossypiumbarbadense plants from the same seed material grown in sterilized soil in clay pots (30 cm) under uniform conditions were placed in a growth chamber with the 4 aqueous solutions mentioned above treated to compare the effects of these different 30 growth regulating compositions. Another group of plants (Group A) served as a comparison. Group A consists of untreated plants; Group B consists of plants treated with compositions of N-methylpyrrolidone and ethephon; Group C consists of plants treated with propylene glycol / ethephon mixtures; Group D consists of plants treated with N-methylpyrrolidone alone and Group E consists of plants treated with ethephon as the active ingredient alone. The amount of the components of the compositions were reported in ppm in one liter of aqueous solution. The experiments were carried out simultaneously and at average temperatures of about 21 ° C. during the day and 13 CC at night, which were maintained in the growth chamber.

Table II shows the relative effect of N-methyl-pyrrolidone / ethephon compositions compared to ethephon alone and ethephon / propylene glycol on opening the capsules on the 8th, 10th and 11th day after spraying.

Table I Opening the Capsules in%

Days after spraying

composition

NMP

E

PG

5

6

7

8th

9

10th

11

12

13

14

15

Comparison A

0

0

0

0

0

9

27th

36

36

36

36

36

36

36

Composition B

1172

3125

0

23

54

62

78

78

85

100

2344

3125

0

0

0

0

40

60

81

90

100

9376

3125

0

0

0

17th

42

58

58

92

100

Composition C.

0

3125

4688

17th

23

30th

46

54

54

54

62

62

62

77

Composition D

2344

0

0

0

0

0

0

0

0

0

0

0

0

0

Composition E

0

3125

0

0

7

27th

46

53

74

87

93

93

100

NMP = N-methylpyrrolidone E = ethephon PG = propylene glycol

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8th

Table II

Relative speed * of opening the capsules

Days after spraying

Composition NMP E PG 8 10 11

Comparison A

0

0

0

0.35

0.42

0.36

Composition B

1172

3125

0

1.00

1.00

1.00

2344

3125

0

0.51

0.94

0.90

9376

3125

0

0.54

0.68

0.92

Composition C

0

3125

4688

0.59

0.64

0.54

Composition D

0

3125

0

0.59

0.87

0.87

* i.e. Percentage or extent of capsules opened

15

The data in Table III show comparisons based on the percentage of capsules ready for harvest obtained from each of the above compositions B to E. as well as comparison A. Capsules ready for harvesting are capsules that are fully open, with the flaps facing downwards, so that the cotton fibers are completely exposed for the pickers.

The data in Table IV provide comparisons based on the relative extent of progression to the capsule ready for harvest

III

based on the use of compositions B, C.E, and comparison A.

Plant cultivation and treatment with compositions B to E and Comparison A were done as described in Example I, except that observations from the days after spraying were limited to the period when the ripe capsules predominate (that is the 10th-13th day after spraying.

Table III% capsules ready for harvest

Days after spraying

composition

NMP

E

PG

10th

12

13-

Comparison A

0

0

0

36

36

36

Composition B

1172

3125

0

39

54

54

2348

3125

0

50

80

100

9376

3125

0

25th

67

67

Composition C

0

3125

4688

23

31

31

Composition D

2344

0

0

0

0

0

Composition E

0

3125

0

27th

40

40

Table IV

Relative speed of promotion to the stage of harvest maturity of the capsules

Days after spraying

Composition of NMP E PG 10 12 13

Comparison A composition B

Composition C Composition E

0 0

1172 3125

2344 3125

9376 3125

0 3125

0 3125

0

0.72

0

0.78

0

1.00

0

0.50

4688

0.45

0

0.54

0.45

0.36

0.68

0.54

1.00

1.00

0.84

0.67

0.39

0.31

0.50

0.40

Example III

The data in Table V show comparisons made on the. The data in Table VI shows comparisons made on the

Percentage of the total activity of the capsules is based, 65 the relative extent of the total activity of the capsules-the popping. Open, opened and ready-to-harvest capsules, which includes compositions B, C and E achieved. what became of each of the above compositions B and comparison A.

until E was reached, as well as comparison A.

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Table V% total activity of the capsules

Days after spraying

composition

NMP

E

PG

5

6

7

8th

9

10th

11

12

13

14

Comparison A

0

0

0

0

9

27th

45

45

45

45

45

45

45

Composition B

1172

3125

0

54

61

77

78

100

2344

3125

0

0

30th

40

60

90

100

9376

3125

0

8th

17th

42

67

91

100

Composition C

0

3125

4688

23

31

45

54

54

62

70

85

85

100

Composition D

2344

0

0

0

0

0

0

0

0

0

0

0

0

Composition E

0

3125

0

7

27th

47

53

87

100

Table VI

% Speed of total activity of the capsules

Days after spraying

composition

NMP

E

PG

6

8th

9

Comparison A

0

0

0

0.15

0.58

0.45

Composition B

1172

3125

0

1.00

1.00

1.00

2344

3125

0

0.49

0.77

0.90

9376

3125

0

0.28

0.86

0.91

Composition C

0

3125

4688

0.51

0.69

0.54

Composition E

0

3125

0

0.44

0.68

0.87

Example IV

The data in Table VII show comparisons based on the percentage leaf drop achieved with compositions B to E and comparison A.

The data in Table VIII show comparisons based on the relative rate of leaf waste obtained from compositions B, C and E and comparison A.

Table VII Leaf waste in percent

Days after spraying

composition

NMP

E

PG

2nd

3rd

4th

5

6

7

8th

9

10th

Comparison A

0

0

0

13

13

16

17th

17th

20th

25th

25th

25th

Composition B

1172

3125

0

17th

26

51

51

64

65

71

84

87

2344

3125

0

29

31

53

57

74

95

96

98

98

9376

3125

0

10th

12

49

63

82

90

90

97

97

Composition C

0

3125

4688

14

18th

39

44

55

63

69

72

75

Composition D

2344

0

0

8th

10th

13

18th

18th

25th

26

26

26

Composition E

0

3125

0

31

43

74

81

88

90

93

94

95

Table VIII Relative speed of leaf waste

Days after spraying

composition

NMP

E

PG

4th

5

6

Comparison A

0

0

0

0.21

0.21

0.20

Composition B

1172

3125

0

0.69

0.63

0.68

2344

3125

0

0.72

0.71

0.84

4688

3125

0

0.66

0.78

0.93

Composition C

0

3125

4688

0.53

0.54

0.61

Composition E

0

3125

0

1.00

1.00

1.00

Two additional compositions were prepared for experiments of the same type as that made with compositions B to E. These additional compositions were obtained by mixing 2344 ppm methyl cellosolve acetate with an aqueous solution of 3125 ppm Ethephon (composition E) and with 7000 ppm S, S, S-tributyl-phosphorotithioate in aqueous solution, which also contains 3125 ppm Ethephon ( Composition G). Compositions F and G, however, killed the plants 3 days after application.

666 990

10th

Example V

The following experiments, which are shown in Tables IX and X, show the effect that high temperatures have on the opening of the capsules in cotton plants.

A. Three groups of 12 week old Gossypium barbaden-se plants from the same seed material grown in sterilized soil in clay pots (30 cc) were tested in a growth chamber for capsule opening and leaf waste. Group A is the comparison group without chemical application; Group B are cotton plants which have been sprayed with the composition according to the invention (B) and Group C are cotton plants which have been sprayed with a composition of ethephon and propylene glycol (C). The results, which are shown in Table IX, represent the average of 4 repeated experiments which were carried out simultaneously for each group. The conditions in the greenhouse were 27 ° C during the day and 15 ° C at night.

The plants, which were subjected to tests in pots, were placed on an elevated grid in order to ensure uniform temperature and humidity conditions. Aqueous solutions containing the compositions of groups B and C in the stated concentration in ppm were sprayed uniformly from above onto the 12-week-old cotton plants at a temperature of about 21 ° C .; the results of this chemical treatment were followed and recorded on the 3rd and 5th day after spraying. The degree and type of effect are shown in Table IX.

Table IX Open the capsules in percent

NMP

PG

ETHE

Days after

PHON

the

TpM

TpM

TpM

spray

3rd day

5.Tas

Comparison A

0

0

0

10th

20th

Composition B

2340

0

1560

0

30th

4688

0

3125

50

50

Composition C

0

2340

1560

0

0

0

4688

3125

25th

50

It was found that higher temperatures caused faster opening.

B. Further experiments with the compositions were carried out in a greenhouse at 35 ° C during the day and 18 ° C at night. The results of these tests on the 5th day after spraying are shown in Table X.

These experiments, like those in Part A, were carried out in double groups for each experimental composition.

Table X Opening the capsules in percent

NMP PG ETHEPHON Day 5 TpM TpM TpM after

spray

Comparison A 0 0 0 58

Composition B 2340 0 1560 80

4688 0 3125 75

Composition C 0 2340 1560 70

0 4688 3125 70

As shown above, the opening of the capsules in the comparison group and by composition B at 35 C is greatly accelerated.

Composition B accelerated the opening of the capsules in the case of immature capsules which contained mature fibers, but left the fully matured, breaking capsules untouched. There was no impairment of the fibers in the fully matured capsules with composition B; the initiation of opening the immature capsules brought improved fiber quality by shortening the resting time in the capsule and thus also the potential time for a fungal infection and by initiating the ripening before the leaf waste, which increased the speed of capsule development with high plant vitality, namely, before the leaf waste interrupted photosynthesis.

Example VI

The comparative experiments described in Table XI show the effect low temperatures have on capsule bursting in cotton plants in the field.

Field trials were carried out at plant distances of 50 cm on 12-week-old cotton plants of the Gos-sypium-hirsutum type, 2 rows of 50 plants serving as a comparison; the same number of plants were treated with composition B (group B); the same number with composition C (group C) and the same number of plants were treated with N-methylpyrrolidone alone, composition D (group D). The temperature varied between 4 ° C during the day and -4 ° C at night. The results are described in Table XI.

Table XI capsule opening in%

NMP

PG

ETHE

Day after

PHON

the

TpM

TpM

TpM

spray

6th day

8th day

Comparison A

0

0

0

0

7

Composition D

9375

0

0

0

0

Composition C

0

4688

3125

22

26

Composition B

4688

0

3125

43

52

In the experiments of Table XI above, it can be seen that composition B greatly reduces the normal resistance of the plants to capsule opening at low temperatures. At a concentration of 3125 ppm Ethephon, composition B causes significantly higher values of the capsule opening of the plant at low temperatures than is the case with composition C. The effect of the leaf waste was not characteristic, since temperatures below freezing naturally cause leaf waste; accordingly, these effects have not been recorded.

In all of the above experiments, the cotton plants sprayed with composition B did not suffer from weakening or shortening of the fibers. Staining both before and after harvest was virtually eliminated, and capsules that developed later, causing opening with the compound of the invention, produced even better fibers.

It can easily be seen from the above data that the composition of N-methylpyrrolidone and β-haloethylphosphonic acid according to the invention is a

5

10th

15

20th

25th

30th

35

40

45

50

55

60

65

11

is a means of harvesting cotton by eliminating the need for separate chemical defoliation and chemical use for popping the capsules and making the metabolic effects more effective to enable higher yield with better cotton quality in a single crop.

The synergistic interaction of the active ingredients is also evident from these values as well as a potential increase in yield during the first harvest. Optimal combinations of the constituents according to the invention within the above ranges can be used in order to meet the requirements of a particular cotton harvest and to eliminate the need for a second harvest.

The commercial advantages of the composition according to the invention and the labor-saving use in the cotton harvest are obvious, since it is possible to plant later and / or harvest earlier in the event of natural crop change.

It should be noted that in the previous examples, each of the other β-haloethylphosphonic

666 990

acids can be used instead of β-chloroethylenephosphonic acid, the same advantages described according to the invention being achieved.

Also in the above examples, a non-cyclic tertiary amide of 3 to 6 carbon atoms, e.g. N, N-dimethylformamide, N, N-dimethylacetamide, etc. can be used in place of N-methylpyrrolidone to achieve increased leaf waste before harvest.

The amides and other compounds described in Table XII below were found to have good defoliation properties when used on cotton plants. The amounts given in Table XII for the respective components of the compositions relate to ppm.

It is shown that each of the following compounds and compositions can be used alone or in combination with the N-methylpyrrolidone / ethephon composition according to the invention in order to intensify the leaf waste in cotton plants.

Table XII

Leaf waste in%

E BLO1 BO2 DMF3 days after spraying

23456789 10

Comparison 0 0 0 0

3125 2344 0 0 3125 0 2344 0 3125 0 0 2344

1. Butyrolactone

2. 2-butynediol

3. N, N-dimethylformamide

13

13

16

17th

17th

20th

25th

25th

25th

29

45

62

68

72

82

82

92

98

23

32

60

66

84

88

97

100

46

56

83

85

91

99

100

The following values show the effect of butyro-lactone-ethephon, butynediol-ethephon and dimethylformamide-ethephon on the activity of the cotton capsules in 15-week-old cotton plants of the Gossypium hir-sutum type.

Plants for 4 replicates were treated in a greenhouse with each of the above mixtures in aqueous solution, spraying each plant at 20 ° C until completely wet. The total capsule activity in percent (including capsule opening, 45 capsule opening and capsules ready for harvest) is given in Table XIII.

Table XIV shows the percentage of capsules ready for harvest for each of the aqueous solutions of the above mixtures.

Tables XIII and XIV show the amounts of the components used in ppm in aqueous solution.

50

Table XIII

BLO B3O DMF% total capsule activity

Days after spraying

5

6

7

8th

9

10th

0

0

0

0

20th

20th

20th

20th

20th

20th

3125

2344

0

0

50

65

75

88

88

88

3125

0

2344

0

86

100

3125

0

0

2344

71

86

72

72

72

72 *

comparison

* 14% of the capsules after 6 days

666 990

12

Table XIV

BLO B30 DMF capsules ready for harvest

Days after spraying

5

6

7

8th

9

10th

0

0

0

0

0

20th

20th

20th

20th

20th

3125

2344

0

0

37

37

50

63

75

88

3125

0

2344

0

58

72

86

93

100

3125

0

0

2344

57

72

72

72

72 *

comparison

14 ° o of the capsules after 6 days

In the following, the same numbers of the examples are also used in the analysis results and the test experiments in order to identify the compound and to explain its use.

Connection:

cich2ch2-

r "

Example No.

R '

R2

R

10th

11

12 15

Connection:

CH, CH, H H

C, H7

CH,

CH,

CH3

H

H

h ch3 ch3 ch3

H

40

Example No.

R1

R5

7

CH,

(CH,),

9

H

(CH:) 3

13

CH,

-CH = CH-CH = CH-

14

CH, -

(CH2) 4

16

&

n X

(CH2) 3

17th

HIGH-.CH-

(CH:) 3

18th

(CH,) -. CH-

(CH2) 3

19th

CfiH ,,

(CH2) 3

20th

(CH,), C-

(CH2) 3

21st

CH3 (CH2) "

(CH2) 3

"■> -)

Polyvinyl

(CH,) 3

pyrrolidone

(K30) complex

60

The above formulas of the compounds or complexes according to the invention have been confirmed by analysis. However, the restrictions already made apply. The same applies to the structural information given in the following examples and tables. In any case, a complex compound is meant which arises in the reaction between 2-chloroethylphosphonic acid or the specified homologous compound and the amide with the meaning given above for R 1, R 2 and R 3.

Example 7

A solution containing 2.97 g (0.03 mol) of N-methyl-2-pyrrolidone in 7.13 g (10 ml) of diethyl ether was stirred with a solution of 4.32 g (0.03 mol ) 2-Chloroethylphosphonic acid in 7.13 g (10 ml) of diethyl ether in a 250 ml Erlenmeyer glass flask equipped with a drying tube (to maintain the anhydrous conditions) and a magnetic stir bar (to ensure continued gentle stirring) was added. The reaction took place at room temperature and atmospheric pressure. Within 10 minutes, 6.48 g of the zwitterionic complex with the structure given above settled out as a yellowish 01 (yield 88.7%). The oil was separated and dried in a rotary evaporator at 50 C and 2 mm for 0.5 hours. The complex was subjected to a combustion analysis without further purification:

Calculated: C = 34.53; H = 6.16; N = 5.75 Found: C = 33.98; H = 6.45; N = 5.74.

The remaining part of the product in the ether phase could be isolated and separated by evaporation of the diethyl ether solvent.

Example 8

A solution containing 3.65 g (0.05 mol) of N, N-dimethylformamide in 7.13 g (10 ml) of diethyl ether was stirred while stirring a solution of 7.23 g (0.05 mol) 2 - Chloroethylphosphonic acid in 7.13 g (10 ml) of diethyl ether in a 250 ml Erlenmeyer glass flask equipped with a drying tube to maintain anhydrous conditions and with a magnetic stir bar to ensure easy stirring. The reaction took place at room temperature and atmospheric pressure.

9.2 g of the above-mentioned zwitterionic complex with the stated structure settled out as a yellowish oil within 10 minutes (yield 84.6%). The oil was separated and dried in a rotary evaporator at 50 C and 20 mm for 0.5 hours. The complex was subjected to a combustion analysis without further purification:

Calculated: C = 27.59: H = 5.98; N = 6.44 Found: C = 24.05: H = 5.36: N = 5.19.

13

666 990

The remaining part of the product in the ether phase could be isolated and separated by evaporation of the diethyl ether solvent.

Example 9

A solution containing 4.25 g (0.05 mol) of 2-pyrrolidone in 7.13 g (10 ml) of diethyl ether was stirred while stirring a solution of 7.23 g (0.05 mol) of 2-chloroethylphosphonic acid in 7 , 13 g (10 ml) of diethyl ether in a 250 ml Erlenmeyer glass flask equipped with a drying tube and a magnetic stir bar. The reaction took place at room temperature and atmospheric pressure. After a few minutes, 10.0 g of the zwitterionic complex with the structure given above settled out as a yellowish oil (yield 87.2%). The oil was separated and dried in a rotary evaporator at 50 ° C and 20 mm for 0.5 hours. The complex was subjected to a combustion analysis without further purification:

Calculated: C = 31.27; H = 5.66; N = 6.10.

Found: C = 30.53; H = 5.74; N = 5.79.

The remaining part of the product in the ether phase could be isolated and separated by evaporation of the diethyl ether solvent.

Example 10

A solution containing 4.35 g (0.05 mol) of N, N-dimethylacetamide in 7.13 g (10 ml) of diethyl ether was stirred while stirring a solution of 7.23 g (0.05 mol) 2 - Chloroethylphosphonic acid in 7.13 g (10 ml) of diethyl ether in a 250 ml Erlenmeyer glass flask equipped with a drying tube and a magnetic stir bar. The reaction took place at room temperature and atmospheric pressure. After a few minutes, 10.4 g of the zwitterionic complex with the structure given above settled out as a yellowish oil. (Yield 89.8%). The oil was separated and dried in a rotary evaporator at 50 ° C and 20 mm for 0.5 hours. The complex was subjected to a combustion analysis without further purification:

Calculated: C = 31.10; H = 6.48; N = 6.05.

Found: C = 28.27; H = 6.19; N = 5.18.

The remaining part of the product in the ether phase can be isolated and separated by evaporating the diethyl ether solvent.

Example 11

A solution containing 3.65 g (0.05 mol) of N-methylacetamide in 7.13 g (10 ml) of diethyl ether was stirred while stirring a solution of 7.23 g (0.05 mol) of 2-chloroethylphosphonic acid in 7 , 13 g (10 ml) of diethyl ether in a 250 ml Erlenmeyer glass flask equipped with a drying tube and a magnetic stir bar. The reaction took place at room temperature and atmospheric pressure. After a few minutes, 10.4 g of the zwitterionic complex with the structure given above settled out as a yellowish oil (yield 95.6%). The oil was separated and dried in a rotary evaporator at 50 "" C and 20 mm for 0.5 hours. The complex was subjected to a combustion analysis without further purification:

Calculated: C = 27.59; H = 5.98; N = 6.44.

Found: C = 26.87; H = 6.02; N = 5.95.

The remaining part of the product in the ether phase could be isolated and separated by evaporation of the diethyl ether solvent.

Example 12

A solution containing 2.95 g (0.05 mol) of acetamide in 7.13 g (10 ml) of diethyl ether was stirred with a solution of 7.23 g (0.05 mol) of 2-chloroethylphosphonic acid in 7.13 g (10 ml) of diethyl ether in a 250 ml Erlenmeyer glass flask equipped with a drying tube and a magnetic stir bar were added. The reaction took place at room temperature and atmospheric pressure. After a few minutes, 10.0 g of the zwitterionic complex shown above settled as a yellowish oil (yield 98.2%). The oil was separated and dried in a rotary evaporator at 50 ° C at 20 mm for 0.5 hours. The complex was subjected to a combustion analysis without further purification:

Calculated: C = 23.59; H = 5.40; N = 6.88.

Found: C = 23.22; H = 5.59; N = 6.74.

The remaining part of the product in the ether phase could be isolated and separated by evaporation of the diethyl ether solvent.

Example 13

A solution containing 3.09 g (0.028 mol) of N-methyl-2-pyridone in 7.13 g (10 ml) of diethyl ether was stirred with a solution of 4.32 g (0.03 mol) of 2-chloroethylphosphonic acid in 7.13 g (10 ml) of diethyl ether in a 250 ml Erlenmeyer glass flask equipped with a drying tube and a magnetic stir bar. The reaction took place at room temperature and atmospheric pressure. After a few minutes, 6.30 g of the zwitterionic complex with the structure shown above settled out as a yellowish oil (yield 87.6%). The oil was separated and dried in a rotary evaporator at 50 ° C and 20 mm for 0.5 hours. The complex was subjected to a combustion analysis without further purification:

Calculated: C = 36.44; H = 5.23; N = 5.19.

Found: C = 37.87; H = 5.13; N = 5.52.

The remaining part of the product in the ether phase could be isolated and separated by evaporation of the diethyl ether solvent.

Example 14

A solution containing 3.39 g (0.03 mol) of N-methyl-2-piperidone in 7.13 g (10 ml) of diethyl ether was stirred with a solution of 4.32 g (0.03 mol ) 2-chloroethylphosphonic acid in 7.13 g (10 ml) of diethyl ether in a 250 ml Erlenmeyer glass flask equipped with a drying tube and a magnetic stir bar. The reaction took place at room temperature and atmospheric pressure. After a few minutes, 5.7 g of the zwitterionic complex with the structure given above settled out as a yellowish oil (yield 73.7%). The oil was separated and dried in a rotary evaporator at 50 ° C and 20 mm for 0.5 hours. The complex was subjected to a combustion analysis without further purification:

Calculated: C = 34.63; H = 6.64; N = 4.80.

Found: C = 37.28; H = 6.60; N = 5.44.

5

10th

15

20th

25th

30th

35

40

45

50

55

60

65

666 990

14

The remaining part of the product in the ether phase could be isolated and separated by evaporation of the diethyl ether solvent.

Example 15 5

A solution containing 4.35 g (0.05 mol) of N-propylformamide in 7.13 g (10 ml) of diethyl ether was stirred with a solution of 7.23 g (0.05 mol) of 2-chloroethylphosphonic acid in 7.13 g (10 ml) of diethyl ether in a 250 ml Erlenmeyer glass flask equipped with a drying tube and a 10 magnetic stir bar. The reaction took place at room temperature and atmospheric pressure. After a few minutes, 10.0 g of the zwitterionic complex shown above settled as a yellowish oil (yield 88.0%). The oil was separated and dried for 0.5 15 hours in a rotary evaporator at 50 ° C and 20 mm. The remaining part of the product could be isolated and separated by evaporation of the diethyl ether solvent.

20th

Example 16

A solution containing 3.50 g (0.02 mol) of N- (o-tolyl) -2-pyrrolidone in 7.13 g (10 ml) of diethyl ether was stirred with a solution of 2.88 g ( 0.02 mol) of 2-chloroethylphosphonic acid in 7.13 g (10 ml) of diethyl ether in a 25 250 ml Erlenmeyer glass flask equipped with a drying tube and a magnetic stir bar were added. The reaction took place at room temperature and atmospheric pressure. After a few minutes, 5.30 g of the zwitterionic complex shown above settled out as a yellowish oil (yield 81.4%). The oil was separated and dried in a rotary evaporator at 50 ° C and 20 mm for 0.5 hours. The remaining part of the product in the ether phase could be isolated and separated by evaporation of the diethyl ether solvent. 35

Example 17

A slurry of 3.87 g (0.03 mol) of N- (2-hydroxyethyl) -2-pyrrolidone was converted to 4.32 g (0.03 mol) of 2-chloroethylphosphonic acid in a 250 ml Er-40 lenmeyer glass flask added. The reaction took place at room temperature and atmospheric pressure. After 30 minutes, 8.19 g of the zwitterionic complex shown above formed in the form of a homogeneous yellowish oil (100% yield). 45

Example 18

A solution containing 2.54 g (0.02 mol) of N- (isopropyl) -2-pyrrolidone in 7.13 g (10 ml) of diethyl ether was stirred with a solution of 2.88 g (0.02 mol ) 2-chloro-50-ethylphosphonic acid in 7.13 g (10 ml) of diethyl ether in a 250 ml Erlenmeyer glass flask equipped with a drying tube and a magnetic stir bar. The reaction took place at room temperature and atmospheric pressure. After 20 minutes, the ether solvent was removed by evaporation and 5.40 g of the zwitterionic complex shown above was obtained as a yellowish oil. The oil was separated off and dried in a rotary evaporator at 50 ° C. and 20 mm for 0.5 hours (yield 100%). 60

Example 19

A solution containing 5.01 g (0.03 mol) of N-cyclohexyl-2-pyrrolidone in 7.13 g (10 ml) of diethyl ether was stirred while stirring a solution of 4.32 g (0.03 mol) 2 -Chlor- 65 ethylphosphonic acid in 7.13 g (10 ml) of diethyl ether in a 250 ml Erlenmeyer glass flask equipped with a drying tube and a magnetic stir bar. The

The reaction took place at room temperature and atmospheric pressure. After 30 minutes, the ether solvent was removed by evaporation under reduced pressure, and 9.30 g of the zwitterionic complex having the structure given above was obtained as a water-insoluble yellowish oil. The oil was separated off and dried in a rotary evaporator at 50 C and 20 mm for 0.5 hours (yield 100%).

Example 20

A solution containing 2.82 g (0.02 mol) of N- (tert-butyl) -2-pyrr-olidone in 7.13 g (10 ml) of diethyl ether was stirred with a solution of 2.88 g (0.05 02 mol) of 2-chloroethylphosphonic acid in 7.13 g (10 ml) of diethyl ether in a 250 ml Erlenmeyer glass flask equipped with a drying tube and a magnetic stir bar. The reaction took place at room temperature and atmospheric pressure. After 20 minutes the ether solvent was evaporated under reduced pressure and 5.40 g of the zwitterionic complex shown above was obtained as a water-insoluble, yellowish oil. The oil was separated and dried in a rotary evaporator at 50 ° C. and 20 mm for 0.5 hours (100% yield).

Example 21

A solution containing 2.54 g (0.01 mol) of N-dodecyl-2-pyrrolidone in 3.57 g (5 ml) of diethyl ether was stirred while stirring a solution of 1.44 g (0.01 mol) 2 - Chloroethylphosphonic acid in 3.57 g (5 ml) of diethyl ether in a 250 ml Erlenmeyer glass flask equipped with a drying tube and a magnetic stir bar. The reaction took place at room temperature and atmospheric pressure. After 20 minutes the ether solvent was evaporated under reduced pressure and 3.40 g of the zwitterionic complex shown above were obtained as a water-insoluble, yellowish oil. The oil was separated and dried in a rotary evaporator at 50 ° C. and 20 mm for 0.5 hours (100% yield).

Example 22

A solution containing 16.5 g (0.15 mol) of polyvinylpyrrolidone (K 30) in 54.6 g of water was stirred with 28.9 g of 2-chloroethylphosphonic acid (GAF "technical grade"), the 21.65 g (0.15 mol) of 2-chloroethylphosphonic acid was added in a 250 ml Erlenmeyer glass flask. The reaction was carried out with stirring at room temperature and atmospheric pressure. After a few minutes, 36.0% by weight of the zwitterionic complex shown on the following page formed in the aqueous solution, which was separated off and dried.

The polymeric product mainly contains the monomer units:

~ Ç 0 yOU N

H-

R

n 0

.p-ch-ch-cl / \ 2 2

—Cn 2— cu — cileno ö- • \ /: i, ch, - p

2 2 / \

no 0-

Oli. • ch-

->

t1 2 -n-r c-r "

n

15

666 990

r3-c = o

2nd

r -n

<-ch ^ ch - cii ^ ch ~

SI — R

0 = c-r

3 years

r "

R

.n o

O, OH \ /

, p-ch, ch, c1 / \

<-cnj- CH-CR-2

m oh ch

S (—R

0 = c-r *

ch.

where each n, m and p is a number between 0 and 500 meaning 2 if n = 0. The monomer units can be tet and where at least one index n and p has a positive 20 in blocks or in random distribution in the polymer, n is at least 1 when p = 0, and p is less.

analysis

The above products were subjected to infrared analysis; the results are shown in Table XV. The shift in the carbonylamide signal shows that the compounds according to the invention are complexes.

Table XV

Product Infrared wavelength from Carbonyl «Instant»

out

Example complex amides non-complex amides difference

Table XVI (continued)

C = O (n)

C = O0i)

(M)

7

6.15

5.95

0.20

8th

6.12

6.01

0.11

9

6.21

5.95

0.26

10th

6.35

6.09

0.26

11

6.30

6.03

0.27

12

6.07

6.03

0.04

13

6.10

6.03

0.07

14

6.33

6.12

0.21

16

6.06

5.89

0.17

17th

6.06

6.02

0.04

18th

6.25

5.95

0.30

19th

6.27

5.97

0.30

20th

6.30

5.93

0.37

21st

6.18

5.93

0.25

The complex structure of the compounds according to the invention was also determined on the basis of the CEPA (2-chloroethylphosphonic acid) concentration in the product by titration in water with NaOH. The CEPA content and the amide content are shown in Table XVI.

Table XVI CEPA content of the products determined by titration in water

Product out

example

Weight percent found CEPA calculated

7

8th

9 10

60.74 66.66 64.53 62.04

59.34 66.44 62.96 62.42

51.46 50.25 51.69 49.60

50.00 50.00 50.00 50.00

Product weight percent from CEPA

30th

35

45

Mol percent CEPA found calculated

Mól percent CEPA

Example found calculated calculated calculated

11

65.35

66.44

48.79

50.00

12

64.67

71.01

42.83

50.00

13

57.30

56.56

50.53

50.00

14

54.07

56.12

47.93

50.00

16

48.22

45.40

52.25

50.00

17th

52.99

52.83

50.16

50.00

18th

53.77

53.39

50.38

50.00

19th

46.98

46.39

50.59

50.00

20th

50.85

50.44

50.06

50.00

21st

36.30

36.51

49.77

50.00

Alcoholic solutions (methanol) of the complex products were also titrated with a standard solution of alcoholic (isopropanol) KOH and compared with methanol solutions of a similar concentration that were titrated with the same standard solution of KOH isopropanol. The titration results are shown in Table XVII on Table XVII comparing CEPA and complex titration with KOH in isopropanol

Product from example

Quay (± 0.

xlO "4)

Ka2

(± 0.07 x 10 "10)

55 8 9

10th

11

12 60 13

14

16

17th

18th

65 19

20th

21st

CEPA

1.26 x 1.41 x 1.07 x 1.00 x 1.26 x 1.32 x 1.12 x 0.83 x 1.31 x 0.79 x 0.98 x 1.00 x 0.89 x 0.76 x 1.20 x

10 "4 IO" 4 10 ~ 4 10 ~ 4 10 ~ 4 IO-4 10-4 IO-4 10-4 10 "4 10" 4 10-4 10 ~ 4 IO "" 4 10-4

1.38x10-1.32 x IO-2.95x10 "0.813 x 10 1.05x10-1.51 x 10" 2.95 x 10 "2.45 x 10" 2.82x10 "1.90x10-3.16 x 10" 3.16x10 "2.24 x 10-1.86x10" 0.86x10 "

666 990

16

and show that there is no significant difference between CEPA and the complex in the dissociation of the first P —OH bond (Kai), but that there is a significant difference between CEPA and the complex in the dissociation of the remaining P —OH bonds (Ka ?) consists. This difference also proves the formation of the complex according to the invention, even if the non-existent difference in the Ka2 value does not indicate the absence of a complex formation.

Biological activity The compounds according to the invention are effective ethylene-releasing agents and, or as such, stimulate the in vivo production of ethylene in plants and plant tissues. Accordingly, these compounds show physiological effects that are characteristic of ethylene. Examples of these effects are well known and include ripening, stunted growth, loss of top dominance, germination, promoting and preventing flowering, and gender reversal in flowers. Leaf senescence, leaf waste, induction of flowering, etc. as in "Ethylene in Plant Biology" by F.B. Abe-les described. Both in laboratory and in field tests, the compounds according to the invention have shown that they promote the in vivo production of ethylene in the field. Some of the compounds according to the invention (based on the molar amount) are more effective simulators than 2-chloroethylphosphonic acid.

Examples 23-35 The ability of the products of the invention to stimulate ethylene production was determined by the following methods:

In a growth chamber, which was kept at 30 C and a light value of 2000 to 3000 foot candles, soybean plants were grown from the same seed material until a single-leaf stage of development. Each of the following experiments was carried out four times and the results (which proved to be highly reproducible) were evaluated on average and recorded in Table XVIII below.

In each of Examples 23-35, 16 samples of leaf sections were removed from the single leaf plant material by cutting the leaf with a round cork borer of known diameter. Each of the 16 leaf disks were then contacted in a closed petri dish with 25 ml of water as a reference or with 25 ml of aqueous solution containing either 1000 rpm (low concentration) or 3000 rpm (high concentration) of the test compound . After 30 minutes, the leaf disks were removed from the solution, dried, and 4 were each placed in four 10 ml vials, each with a septum through which a syringe could be inserted, to take a sample of the atmosphere above the water , were equipped. Four repeated gas samples were taken for each compound after the samples were in the light for 1 hour. The samples were analyzed for their ethylene content by gas chromatography. The vials were then placed in the dark for 15 hours; after this time the gas above the leaf sections was again sampled and analyzed in the same way as described previously. The results, which are based on a comparison with the comparative sample, are summarized in Table XVIII, namely in nanoliter ethylene per liter atmosphere per cm2 of the leaf surface and per mmol of the test compound: they relate to the average of the 4 repeated samples.

Table XVIII

At

connection

Concentrate

Nano-1

Ethylene / l / cm2 / mmol play from example tration

1 hour (a) 15 hours (b)

x 103

x 103

23

7

low

6,720

21.904

high

6,690

17,496

24th

8th

low

2,923

11.824

high

2,842

12,300

25th

9

low

4,202

16,919

high

2,859

13.863

26

10th

low

2,800

13,273

high

3,701

14.923

27th

11

low

2,195

14,586

high

3,631

16.078

28

12

low

913

8,365

high

2,542

11.520

29

13

low

4,368

15,647

high

4,991

14.681

30th

14

low

4,282

11.850

high

4,603

18,988

31

16

low

3,379

15.311

high

6,912

15,268

32

17th

low

3,563

16.654

high

4,412

15,295

33

18th

low

3,743

15,090

high

4.805

14.264

34

22

low

4,679

18.726

high

5,223

16,689

35

2-chloroethyl low

4,912

15,944

high phosphonic acid

4,876

14.035

low = 1,000 ppm high = 3,000 ppm single-leaf plants a. in the light b. in the dark c. untreated tissue (comparison) gave 125 nano-1 ethylene / l / cm2 after 1 hour and 180 nano-1 ethylene / l / cm2 after 16 hours.

Examples 35-38

As a comparison between compound 7 and 2-chloroethylphosphonic acid (CEPA), a field test was carried out to check whether these compounds have the ability to transform ripe, green, smoke-dried tobacco leaves into yellow, mature ones. The results of this experiment are given in Table IXX.

On the field, 7 separate parcels, each containing an average of 50 tobacco plants that grew under the same conditions, were used for test purposes. The first 2 plots were sprayed with an aqueous solution of CEPA in an amount of 0.0077 kg mol / ha; the average results are shown in Table IXX as parcel 1.

A further 2 plots were sprayed with an aqueous solution of CEPA in the same concentration in an amount of 0.01540 kg mol ha (this is the usual standard amount for the use of CEPA) and the average results are shown in Table IXX as parcel 2.

A further 2 plots were flue-cured with an aqueous solution of the complex product from Example 7 in the same concentration as above in an amount of 0.00836 kg mol / ha

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17 666 990

sprayed; the average results are shown in table. The last plot was treated untreated as a comparison.

IXX indicated as parcel 3. to let.

Table IXX

Example number

Parcel number

CEPA connection from days after the yield of

kgmol / ha Example 7 Treatment for Dried Tobacco kg mol / ha Production of kg / ha

Harvest maturity

35

36

37

38

1

2nd

3rd

comparison

0.00770 0.01540 0 0

0 0

0.00836 0

15 4 4 21

2927 2357 2520 2971

It is very important that the treatment with the compound from Example 7 gave a 7% higher yield than the treatment with 2-chloroethylphosphonic acid (parcel 2), where the conventional standard amount for 2-20 chloroethylphosphonic acid was used; a mature crop was also obtained in only a quarter of the time required for CEPA when CEPA and the compound from Example 7 were used in substantially the same amount. 25th

If the compounds according to the invention, e.g. the compounds of Examples 7 and 14 in a concentration of about 3000 ppm in aqueous solution are sprayed onto long, narrow plants during the growth stage until the liquid runs down (e.g. ornamental plants such as 30 Chrysanthenum or a species of the grass family such as corn) a considerable growth inhibition (10-25%) was found in the mature plants. The compounds according to the invention have many other properties which regulate plant growth, which are known and which are attributed to the influence of ethylene. These effects are achieved by the ethylene-releasing properties of the compound according to the invention.

Example 39 40

Reddening of apples Four repeating groups of fruit-bearing “Cornell Mclntosh” apple trees were sprayed with the solutions listed in Table XX below so that the liquid ran down. Another same group 45 of trees remained untreated for comparison. After a week, the apples were harvested and the visible values determined. The average of the results is as follows:

Table XX 50

Treatment amount% red color mmol / 1

none - 36 55

Ethephon 0.248 63

Ethephon 0.497 67

NMP / CEPA complex 0.270 69

NMP / CEPA complex 0.540 74

60

NMP = N-methyl-2-pyrrolidone and CEPA = 2-chloroethylphosphonic acid

Example 40 Reddening of Apples Three groups of 4 year old "Millersturdeespur" apple trees (5 in each group) were sprayed with the aqueous solutions described in Table XXI below until the liquid ran down. Another group of five 4 year old trees were left untreated for comparison.

After 2 weeks, the apples were harvested and evaluated. The average results are as follows:

Table XXI

Treatment amount% red color mmol / I

none - 33.3

Ethephon 0.248 38.1

Ethephon 0.497 58.4

NMP / CEPA complex 0.270 64.2

NMP and CEPA are as defined above.

Example 41 Loosening of Walnuts Two groups of “Ashley” walnut trees bearing load were sprayed in such a way that the aqueous solutions described in Table XXII ran off. Another group of 5 trees was left untreated for comparison. The following average results were obtained after 10 days:

Table XXII

Treatment Amount of leaf waste Harvestability mmol / 3.78 1% removable none - 0.0 50.0

Ethephon 0.0145 3.0 99.5 NMP / CEPA-

Complex 0.0078 1.2 86.0

NMP and CEPA are as defined above.

It has been found that 1.03 mmol / 1 ethephon is required to redden 72% of Cornell McIntosh apples when treated similarly (see Table II of the publication in The Journal of American Society for Horticultural Science, Volume 99 No. 3, p. 239, May 1974).

65 When evaluating leaf waste, 3 means excessive waste, 1 light waste that is not harmful to the tree. Harvestability values in the table above were obtained during normal harvest.

666 990

18th

Example 42 Loosening sour cherries In two groups of fruit-bearing "Montmorency" sour cherry trees (3 trees in each group) the branches were sprayed so that the aqueous solutions described in Table XXIII ran off. Another group of 3 trees remained untreated as a comparison. After one week, the following averages were calculated. The measurements of the force required to remove the fruit were carried out on 100 fruit per test group after 7 days.

Table XXIII

Treatment Amount of force required to remove mmol / 1 of fruit, N

none - 4.36

Ethephon 1.375 2.76

NMP / CEPA complex 0.716 2.73

NMP and CEPA = as defined above.

The above field tests show that about twice as much ethephon is required to obtain a result that is equivalent to that of the complex according to the invention.

Example 43 Loosening Hazelnuts In 4 groups of nut-bearing "Barcellona" hazelnut trees (5 trees in each group) the branches were sprayed until the aqueous solutions listed in Table XXIV ran down. Another group of 5 trees was not treated as a comparison. The following average results were obtained after 2 weeks:

Table XXIV

Treatment amount% waste

Mol / 378 1

none - 13.8

Ethephon 1.31 30.7

Ethephon 2.61 42.9

NMP / CEPA complex 1.87 50.8

NMP / CEPA complex 2.82 55.0

NMP and CEPA = as defined above.

Example 44 Intensification of Color in Grapes 4 groups of fruit-bearing vines +) (5 vines in each group) were sprayed with the aqueous solutions given in Table XXV until they ran off. Another group of 5 vines remained untreated as a comparison.

The grapes were harvested when the comparison "brix" number was 22; then the grapes were juiced. Optical density measurements could be carried out on the solutions obtained. The average number of repeated attempts is as follows:

1 "Zinfandel"

Table XXV

Treatment amount% color

Mol / 1

none - 50

Ethephon 3.93 91

NMP / CEPA complex 2.45 100

NMP / CEPA complex 0.67 71

NMP / CEPA complex 0.09 39

NMP and CEPA = as defined above.

Example 45

Experiments with gender characteristics in cucumbers Two groups of "Galaxy" cucumber plants (2 plants in each group) were sprayed with the aqueous solutions listed in Table XXVI after the first actual leaf stage occurred until the liquid ran down. Another group of 2 plants was not treated as a comparison. The results were averaged and were as follows:

Table XXVI

Treatment amount ratio internode

mmol / 1 of male / distance * cm female Flowers no

_

38.6

144

Ethephon

0.0412

8.8

131

Ethephon

0.1237

4.1

123

NMP / CEPA-

complex

0.0445

3.4

117

NMP / CEPA-

complex

0.1336

1.3

105

NMP and CEPA = as defined above.

* Total distance from 1-15 internodia.

It is noted that in the above examples, the other haloalkylphosphonic acids encompassed by formula (10), e.g. the fluorine, chlorine, bromine or iodomethyl, ethyl, propyl or butylphosphonic acids in Examples 7 to 22 can also be used to give the corresponding complex product, and that the product thus obtained at any of the above examples demonstrating biological effects can be used to form compositions with similar uses.

Furthermore, all amides which the formula (20) comprises, such as: N, N-diethylbutyramide, N-propylbutyramide, propamide, N-methylpropamide, N-methylacetamide, N, N-dimethylacetamide, acetamide, N, N-dimethylformamide, N -Ethylacetamide, N-butylacetamide, N-ethylpyrrolidone, N-methylpyrrolidone, N-butylpyrrolidone, N-ethylpyridone, N-methylpyridone, N-propylpyridone, 2-pyrrolone, N-methylpyrrolone, N, N'-dimethylantipyrin Methylpiperidone, N-ethylpiperidone, N-naphthyl-2-piperidone, 2-piperidone, N-butylpiperidone, N-hydroxyethylpyrrolidone, N-isooctyl-pyrrolidone, N-isopropylpyrrolidone, N- (o-tolyl) -pyrrolidone, N Trichloroethyl) pyrrolidone, polyvinyl pyrrolidone with an average molecular weight between about 20,000 and about 550,000, furthermore: vinyl 2-pyrrolidone dimer, trimer or tetramer, N-dodecylpyrrolidone, N-cyclohexylpyrrolidone, N-phenylpyrrolidone, N- (2-chlorophore

5

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20th

25th

30th

35

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50

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65

nyl) -2-pyrrolidone, N-naphthylpyrrolidone, etc. can be used in Examples 7 to 22 above. Furthermore, another haloalkylphosphonic acid can be used in these examples to obtain a corresponding Ver666 990

to form a bond. The resulting product can be used in any of the above examples showing biological effects to create preparations of similar utility.

19th

5

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25th

30th

35

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45

50

55

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65

S

Claims (15)

666 990 1 H 1 p ' I. 0 1 0 h ch. + ' .0 n -CH; ch. CH ". * ch, 2. The method according to claim 1, characterized in that a heterocyclic or linear monoamide is used as compound (b1). 2nd PATENT CLAIMS 1. Process for the preparation of a plant treatment agent, characterized in that the following compounds (a) and (b), which can react with one another in a complex-forming manner, are brought into contact with one another: (a) a haloalkylphosphonic acid of the formula (10) xr 3rd 666 990 cich2ch2- CH; ch, ch. (3) 3. The method according to claim 1, characterized in that as compound (b) poly (N-vinyl-2-pyrrolidone), N-methyl-2-pyrrolidone, N-methyl-2-pyridone, N-methyl-2- piperidone, N, N-dimethylformamide or acetamide are used. (4) c1ch2ch2- H " 0 p 4. The method according to claim 2, characterized in that a monoamide (b1) with an unsaturated or saturated heterocycle is used as the compound (b). 5 - Uh. H 0 C ch, (5) cich2ch2- ctt ch CH ■ ch 5. The method according to any one of claims 1 to 4, characterized in that the compounds (a) and (b) are allowed to react with one another in a complex-forming manner in the presence of an organic solvent and the solvent is selected so that the solvent and the product in the reaction mixture each form a separate layer when the reaction is complete and that the product is obtained by phase separation. (6) cic »2ch2- h t 0 6. The method according to any one of claims 1 to 4, characterized in that it is carried out in the presence of water and the product is obtained by evaporating the water or by phase separation. (7) cich2ch2- N (CH,) - H J £ CH 7. The method according to claim 1, characterized in that as compounds (a) and (b) chloroethylphosphonic acid and N-methyl-2-pyrrolidone are used and the plant treatment agent contains water as a carrier. (8th) 8. Plant treatment agents obtained by the process according to claim 1. 9. Composition according to claim 8, characterized in that it is a complex compound of the formula (1) R n ch .0 ch. contains, or (b3) is the N-cyclohexyl-2-pyrrolidone or the N- (2-chlorophenyl) -2-pyrrolidone. in which X, R, R ', R2 and R3 have the meaning given in Claim 1, or a polymer of such a compound in which R1, R2 and R3 have the meaning given in Claim 1 under (b2), or contains the product of intermolecular neutralization of such a compound. 10. Composition according to claim 9, characterized in that l 4 U) that XR is haloethyl, R1 is the hydrogen atom or the methyl group and R2 and R3 together represent a divalent group which together with the N atom which is in the Formula (1) carries a positive charge, and the carbon atom bound by a double bond to this N atom forms an N-heterocyclic ring having 4 or 5 carbon atoms. 55 11. Composition according to claim 9, characterized in that the compound of the formula (1) corresponds to one of the formulas (3) to (8): c1ch2ch2- (10) in which X represents a halogen atom and R represents a divalent lower alkane radical, and is (b) a nitrogen compound which (b1) is one of the formula (20) O II c (20) 20th in which R1, R2 and R3 independently of one another denote hydrogen, 25 phenyl, naphthyl, lower alkyl-substituted phenyl or unsubstituted or substituted by hydroxyl or halogen-substituted alkyl having 1-24 carbon atoms, where R1 can also be an alkenyl group having 2-6 carbon atoms and / or R2 and R3 together can form a divalent group, which together with the N atom to which R1 and R2 are bonded and the carbon atom bonded to this N atom and to R3 form a heterocyclic ring with 3 - 5 carbon atoms, or (b2) a polymer of a compound of formula (20) in which R 'is vinyl and R2 and R3 together represent a divalent group which together with the N atom to which R1 and R2 are attached and to which this N atom and carbon atom bonded to R3 forms a heterocyclic ring with 3-5 carbon atoms, which polymer repeating units of the formula (40) 12. A process for regulating plant growth, characterized in that the plants or their cultivated area are treated with an agent which is prepared by the process according to one of claims 1 to 7. 13. The method according to claim 12, characterized in that the agent is applied in an aqueous medium to the plants or the acreage. 14. The method according to claim 12, characterized in that the agent is applied in a mixture with an inert, anhydrous carrier to the plants or the acreage. 15. The method according to claim 12, characterized in that the plants or their acreage are treated with egg-60 nem obtained from chloroethylphosphonic acid and N-methyl-2-pyrrole-don, which contains water as a carrier.