DE2352661C3 - 3,4-dihydro-2H-pyran-2,4-diones and their metal salts and their use as herbicides or plant growth regulators - Google Patents

Description

The invention relates to 3,4-dihydro-2H-pyran-2,4-diones of the general formula:

NH-OR ₃

Ri O O

in which Ri and R _{2 are} alkyl groups with 1 to 4 carbon atoms, R3 is an alkyl group with 1 to 4 carbon atoms, an allyl or a propargyl group and X is a hydrogen or bromine atom, but R | and R ₂ do not both represent a methyl group at the same time, as well as their metal salts and their use as herbicides or plant growth regulators.

From JA-PS 16 916/1971 are 4-hydroxy-6-nriethyl-Λ-pyrone derivatives known to have herbicidal properties.

However, in order to completely eradicate grass-like weeds, these known compounds must be very large Amount can be applied, which is disadvantageous in various respects.

As can be seen from this patent and as confirmed by additional tests, are known active ingredients in quantities of 500 g per 10Ar practically usable as herbicides, however, they result in amounts of e.g. B. 250 g / are no longer completely killing the weeds.

It has now been found that the 3,4-dihydro-2H-pyi'an-2,4-diones according to the invention of the abovementioned general formula and their metal salts have a better effectiveness than the known compounds. With the compounds according to the invention, amounts of 125 g or less to a Area of 10 ares gives excellent results.

Surprisingly, some of the compounds of the invention show when used against grass growth (barnyard grass) together with a damp treatment of the soil is about 30 times higher Herbicidal activity than the known means.

The compounds of the present invention are particularly effective as herbicides selective for grassy ones Weeds such as ring-shaped blue grass (Poa annua), water foxtail (Alopecurus aequalis) or large ones Fingergrass (Digitaria adscendens), which is applied through the soil or through the leaves.

When using the compounds according to the invention for treating the leaves, can be broad-leaved plants, such as radish, soybean (Glycine max), garden pea (Pisum sativum), spinach (Spinacia oleracea) and sugar beets do not observe any damage if you use amounts that are disruptive Kill grass growth completely. When treating the soil before germination, the seeds are removed from porridge-leaved plants are not affected at all if you apply amounts of herbicides which, for. B. that Sprouting of large fingergrass (also known as "large foxtail") (Digitaria adscendens) completely prevent.

The phytotoxicity to broad-leaved plants is, if there are any, extremely low. It is therefore possible to use the compounds according to the invention in terms of application time, of location and concentration to vary within very wide limits.

Another important effect of the compounds according to the invention is that they in many cases Cause dwarfism, especially when applying them to lawns, thereby reducing the harmful side effects too frequent cutting of the lawn can be avoided. It is particularly in the garden and on golf courses This control of the grass growth is very important because it involves a relatively large amount of work can avoid and the disadvantages of too frequent cutting on the appearance of the lawn Appearance.

The compounds according to the invention serve as active ingredients for regulating plant growth and especially the formation of new buds or unwanted side shoots without the leaves and Stems of broad-leaved plants can be damaged, even if the compounds are in larger quantities be used. The aforementioned regulation effect can, for. B. be used to suppress Side shoots in tobacco and chrysanthemum plants or to prevent fruit trees or beans shoot too hard. Effects that are special in the various useful and ornamental plants Are worth.

Another advantage of the compounds according to the invention is that neither a permanent Toxicity in the soil or in the plant adds an acute toxicity to warm-blooded animals and fish it is to be feared that the compounds can be used in very low concentrations.

In the following comparative experiments, the effect of compounds according to the invention was compared with the 3- (N-ethoxyacetimidoyl) -4-hydroxy-6-methyl- (X-pyrone) known from JA-PS 16 916/1971 (Experiments 1 to 8) and its calcium salt (experiments 10 to 13) checked.

Attempt I.
Preventing weed seeds from germinating

Soil containing a mixture of seeds from various foxtail species and cabbage purslane was placed in a pot with a surface area of ^{780 cm 2.} Then, according to Example 11, a powder was prepared with the active ingredient in question, which was diluted with water to a certain concentration, whereupon the earth was sprayed with the diluted aqueous suspension in order to prevent the weed seeds from germinating. Weed growth was examined during the 25th day after spraying. The test results were evaluated according to the following standard, which has the following meaning:

- no effect

- some light brown spots

- Significant damage to the leaves - some leaves and parts of the stems partially dead

- Plant partially destroyed

- Plant completely destroyed or no germination.

The results are shown in Table 11.

Table II

test Active ingredient State of plant Cabbage connection crowd greater smoother
Fox ponulak Fox tail (g / 10a) tail

35

250 5 125 5 62.5 5 250 5 125 5 62.5 5 250 5 125 5 62.5 5 250 5 125 5 62.5 5 250 5 125 5 62.5 5 250 5 125 5 62.5 5 250 5 125 5 62.5 4th 250 5 125 5 62.5 5 250 5 125 5 62.5 5 250 5 125 5 62.5 4th 250 5 125 5 62.5 5

2 0 0 1

0 0 2 0 0 2 1 0 2 0 0 2 0 0 2 0 0 2 0 0 2 1

0 2 0 0 ι

0 2 1

0 2 1

0 2 1

0 1 1

0 2 0 0 2 1

0 2 1

0 2 1

0 2 1

0 2

Connection

Active ingredient

crowd

(g / IOii)

Condition of plants

large foxtail

smooth foxtail

Cabbage purslane

250
125

62.5
250
125

62.5
250
125

62.5
250
125

62.5
250
125

62.5
250
125

62.5
250
125

62.5

Comparison 250
connection 125

62.5
U.N-

treated
floor

5 5 5 5 5 5 5 5 4 5 5 5 5 5 5 5 5 5 5 5 5 5 5 3

0 0 I.

0 0 1

0 0 2 1

0 1 1

0 1 1

0 1 1

0 0

attempt

Treatment of the leaves

The soil was poured into a pot with a surface area of 780 cm ² , whereupon the seeds of two foxtail species were sown and lightly covered with soil. The pots were taken to the greenhouse. Between the development of the second and fourth leaves, an aqueous suspension with the active ingredient in question was prepared according to Example 11 and this was sprayed in an amount of 1001/10 ares onto the stems and leaves of the test plants. Three weeks after the spraying, the condition of the plants was examined. The results are given in Table 111, the grading being an experiment.

55

Table III Active ingredient Condition of plants smoother Tcst- mengc Fox denial greater tail Foxtail 0 (g / 10a) 0 500 4th 0 1 250 4th 0 125 2 0 500 4th 0 2 250 3 0 125 2 0 500 4th 0 3 250 4th 125 2

continuation

Tesa connection

Effective volume

(g / 10a)

500 250 125 500 250 125 500 250 125 500 250 125 500 250 125 500 250 125 500 250 125 500 250 125 500 250 125 500 250 125 500 250 125 500 250 125 500 250 125 500 250 125 500 250 125

Comparative 500

binding 250

125

Unbchiindcli -

Table V

Test connection

Amount of material (g / 1 Oh)

150 150 150 150

Condition of the plants

big smoother

Fox swan / fox tail

5 4 3 4 4 3 5 4 3 4 3 2 5 5 4 5 4 4 5 5 4 5 4 3 5 4 3 4 4 3 5 4 4 5 4 4 5 4 3 5 4 3 4 4 3 3 2

(inisMitiien

0 0 0 0 0 0 0 0 0 2 0 0 2 1 0 2 1

0 1

0 0 1 0 0 1

0 0 1

0 0 1

0 0 1

0 0 1

0 0 2 0 0 1

0 0 0 0 0 0 Attempt 3
Treatment of the earth

About 1 g of grass seed (Barnyard grass) was sown in soil in a flower pot and the Moved the pot to the greenhouse after lightly covering it with soil. As far as the seeds at all germinated and the grass plants had formed the first leaf, the pot was placed in water, the to was kept permanently at a depth of 3 cm and the pot was filled with a dilute aqueous Suspension, which contained a certain amount of active ingredient, watered. 14 days after treatment, the State of the grass plants examined. The results are in Table IV, according to the standard of evaluation from experiment 1. Table IV

Test connection

Amount of active ingredient (g / 10a) 62.5 31.3

Comparison connection
Untreated

5
5
5
5
5
5
5
5
5
5
5
5
4th
5

C.
■ J

5
5
5
3

5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5

3 5 4 5 4 4 3 5 4 3 4 5 3 5 5 5 3 4 0

Attempt 4

Determination of the Selective Effect Again pots ^{with a surface area of 780 cm 2} with soil were used, into which seeds of grass, green beans, radishes, cucumbers, beets and tomatoes were introduced

became. After covering with earth, the pots were taken to the greenhouse. As far as the plants reached a height of 5 to 8 cm, they were sprayed with an emulsifiable concentrate according to Example 13 (1001 / 10a) which contained the relevant compounds. Two

Weeks after treatment, the condition of the plants was assessed according to the scale of Experiment I. The results are shown in Table V.

Hrcilblaltpflatr / .en Kilbe: cucumber

radish

0
0
0
0

rule you [OIIUIILM 0 0 0 0 0 0 0 0

continuation Werkstorf
crowd
(g / l Oa) Grass seeds Leaf plants
Beet cucumber Delicious Red beans * test
connection tomatoes

5 150 5 0 0 0 0 0 6th 150 4th 0 0 0 0 0 9 150 4th 0 0 0 0 0 11th 150 5 1 0 0 0 0 14th 150 5 0 0 0 1 0 15th 150 4th 0 0 0 0 0 17th 150 5 0 0 0 0 0 18th 150 5 0 0 0 0 0 19th 150 4th 0 0 0 0 0 20th 150 5 0 0 0 0 0 21 150 5 0 0 0 1 0 22nd 150 5 0 0 0 0 0 23 150 5 0 0 0 0 1 25th 150 4th 0 0 0 0 0 Comparison 150 3 0 0 0 0 0 connection Untreated - 0 0 0 0 0 0

Attempt to prevent weed seeds from germinating

Large foxtail and cabbage purslane were sown in a pot with a surface area of 10 × 10 cm ² and the potting soil was immediately sprayed with an emulsifiable concentrate of the test compound in question, which had been prepared according to Example 13 and diluted accordingly. The condition of the emerged plants was examined 21 days after the spraying. The grading was carried out according to the experiment. The results are shown in Table VI.

35

Table Vl

test Amount of active ingredient Status Cabbage connection greater purslane Fox (g / IOH) tail

500 250 125 500 250 125 500 250 125 500 250 125 500 250 125

Comparison 500 connection 250

125

40

45 attempt 6
Treatment of the leaves

Seeds of yard grass and smooth foxtail were sown in pots and lightly covered with earth, whereupon the pots were brought into the greenhouse. As far as the seeds have sprouted and the little plants up had grown to spread the first leaf, an emulsifiable one prepared according to Example 13 became Concentrate of the test compound after dilution with water to a specific concentration Stems and leaves sprayed on. Two weeks after the spraying, the condition of the plants became tested and graded according to experiment 1. The results are shown in Table VII.

Table VIl

Tcst connection Amount of active ingredient

(g / 10a)

State ilofgrns

30th 500 250 125 31 500 250 125 32 500 250 125 34 500 250 125 Comparison 500 connection 250 125

5 5 5 5 4 5 3 2

smooth foxtail

0 708 639/323

* Experiment 7

Treatment of the potting soil

About 1 g of yard grass seeds were placed in pots sown and immediately covered with earth, whereupon the pots were brought into the greenhouse. So much for the seeds had risen and the plantlets had grown until the first leaf had spread, the pots were in Water kept constant at a depth of 3 cm, adjusted, followed by an emulsifiable concentrate the relevant test compound prepared according to Example 13 in an appropriate dilution to the Pots has been poured. 14 and 21 days after the treatment, the growth state of the plantlets became determined and graded according to experiment 1.

The results are shown in Table VIII.

Table VIII

Test connection

Amount of active ingredient
(g / 10a)

State 14th day

21st day

200 100

50 200 100

50 200 100

50

5 5 5 5 5 5 5 5 5

Test connection

Amount of active ingredient (g / 1 Oa)

State 14th day

21st day

33 200 5 Trial 8 5 100 5 5 50 5 5 34 200 5 5 100 5 5 50 5 5 Comparison 200 5 5 connection 100 4th 4th 50 2 2

Selective herbicidal action

In soil in vessels with a ^{surface area of 780 cm 2} , seeds of barnyard grass, red beans, radishes, cucumbers, beets, tomatoes and soybeans were sown and lightly covered with earth, after which the vessels were brought into the greenhouse. As far as the seeds had sprouted and the plants had a height of about 5 to 8 cm, an emulsifiable concentrate prepared according to the example with the test compound in question, appropriately diluted with water, was sprayed onto the stems and leaves of the plants, the amount of diluted emulsion being 100 I / 10a. 10 days after the treatment, the condition of the little plants was evaluated according to the standard given in the experiment.

The results are shown in Table IX.

Table IX

connection
No.

Compare connection

Amount of active ingredient

(g / 10a)

150
150
150
150
150
150

Grasses broadleaf plants yard grass red beans radish

0 0 0 0 0 0 cucumbers beets

4th 3 4th 3 0

Tomato soybean

5 5 4 2 4 0

0 0 0 0 0 0

Attempt 9

Table X

Growth control c for lawns

Pieces of lawn (variety: Highland bent) of 9 cm Diameters at a certain stage of growth were mowed with a small lawnmower. that their height was about 1.5 cm.

On the second day after the struggle, a do M) emulsifiable concentrate of the test compound, which was prepared in accordance with Example 13 and appropriately diluted with water, was sprayed onto the lawn pieces so that the amount of active ingredient was 100 I / 100a. The height of the grass plants was determined 5 and 12 days after the spraying. The results are shown in Table X. The experiment was repeated three times.

connection

Efficiency mcngc

Ii)

llnbchiiiuleli -

Height of grass plants in cm

5th tug 12th day

me treatment

1.6 1.8 1.7 1.5 1.4 1.7 3.8 3.5 3.8

1.9 2.1 1.9 1.7 1.7 2.0 7.0 7.5 7.0

<r

Attempt 10
Preventing weeds from germinating and sprouting

In pots with a surface area of 10 χ 10 cm ² , a mixture of seeds of large foxtail and cabbage purslane was sown. A wettable powder with the test compound, which was prepared according to Example 11, was immediately over the seeds covered with soil and diluted with water to form a suspension was sprayed on. 21 days after the spraying, the condition of the plants was determined and graded according to experiment 1.

The results are shown in Table Xl.

Table XI Active ingredient attempt Status Cabbage test crowd purslane connection no. greater 1 (g / 1 Oa) Foxtail 0 250 5 0 38 125 5 2 62.5 4th 1 250 5 0 41 125 5 2 62.5 4th 1 250 5 0 43 125 5 2 62.5 5 1 250 5 0 44 125 5 1 62.5 5 0 250 5 0 45 125 5 2 62.5 4th 0 250 5 0 47 125 5 1 62.5 5 1 250 5 0 Comparison 125 3 connection 62.5 1 11th

Treatment of the earth in standing water

About 1 g of seeds of farm grass were sown in pots with soil and lightly covered with soil, whereupon the pots were moved to the greenhouse. As far as the seed had germinated and the plants up to Spreading the first leaf, the pots were placed 3 cm deep in standing water. At the same time, a wettable powder of the relevant Test compound, which was prepared according to Example 11 and diluted with water, as The same amount of suspension is poured onto the pot. 14 days after the treatment, the Condition of the grass plants determined and graded according to experiment 1. The results are shown in Table XII emerged.

Table XII Connection no.

Amount of active ingredient (g / IOa) I2S I) 2, p

31.5

36 5 5 4th 37 5 5 4th 39 5 5 4th

Connection no.

Amount of active ingredient (g / tOa) 125 62.5

40 5 5 Attempt 12 4th 42 5 5 5 43 5 5 4th 44 5 5 5 46 5 5 5 48 5 5 5 51 5 5 5 Comparison 5 3 1 connection

Treatment by spraying the leaves

Seeds of yard grass and smooth foxtail were sown in pots that were placed in the greenhouse were spent. As far as the seeds had germinated and the little plants until the first leaf had spread had grown, they were treated with a suspension of the respective test compound in a certain concentration, which was produced according to Example 11 (1001 / 10a) sprayed. 2 weeks after the spraying, the condition of the plants was determined and according to the experiment graded. The results are shown in Table XIII.

Table XIII

35

connection Active ingredient Status smoother No. crowd Fox Yard grass tail (g / 10a)

45

39 42 46 47 48 51

55 Vcrgleiehsvcrbindting

500
250
125
500
250
125
500
250
125
500
250
125
500
250
125
500
250
125

500 250 125

0 0 0 1

0 0 1

0 0 0 0 0 2 0 0 0 0 0 0 0 0

Trial 13
Selective herbicidal action

Seeds ν farm grass, red beans, radishes, cucumbers, beets and tomatoes were sown in vessels with a ^{surface area of 780 cm 2 and lightly covered with earth, after which the vessels were brought into the greenhouse.} So the sprouted plants a height of 5 to

reached, they were once with a suspension the respective test compound (prepared according to Example 11 and by diluting with water to a brought certain concentration) sprayed (1001 /

Table XIV

10a). 10 days after the spraying, the condition became the plantlets examined and graded according to experiment 1. The results are shown in Table XIV.

Connection no.

Amount of active ingredient
(g / 10a)

Broadleaf grasses

Hofgras red bean radish

Cucumber

Beets

tomatoes

36 150 40 150 42 150 46 150 47 150 5 150 Comparison 150 connection Untreated

5 5 4 4 5 5 3

0 0 0 0 0 0 0

0 0 0 0 0 0 0

0 0 0 0 0 1

0 0 0 0 0 0

Experiment 14 Influencing the growth of lawns

Lawn (variety: Highland-Bent) in pots of 9 cm was shortened to a height of 1.5 cm. 2 days after cutting, the lawn was covered with one according to the example 11 prepared suspension with the test compound in question by diluting with water a certain concentration was set, sprayed. The diluted solution was in a lot applied by 1001/1 Oa. The height of the lawn was determined 5 and 12 days after the spraying. the Results are shown in Table XV. The experiment was repeated three times.

Table XV Active ingredient Height of Grass in cm connection crowd No. after after (g / 10a) 5 days 12 days 100 1.3 1.6 37 1.5 1.9 1.5 1.8 100 1.4 1.6 41 1.4 1.8 1.5 1.8 100 1.4 1.6 51 1.3 1.5 1.5 1.8 - 3.8 7.0 Untreated 3.5 7.5 3.8 7.0

The compounds according to the invention of the general formula given above are thereby produced that in a known manner a compound of the general formula

(1)

with an amino compound of the general formula NH ₂ -O- R3, where in the formulas Ri, R2, R ₃ and X have the above meaning and the 3,4-dihydro-2H-pyran-2,4-dione obtained optionally converted into a metal salt.

The reaction is carried out in an inert solvent.

Acetone, ether, methyl alcohol, ethyl alcohol, isopropyl alcohol, benzene, Dimethylformamide, chloroform, acetonitrile, dichloroethane, dichloromethane, ethyl acetate, dioxane, toluene, Xylene and dimethyl sulfoxide, preferably methyl, ethyl and isopropyl alcohol, acetonitrile, dimethylformamide, Dioxane, ether and chloroform are used

Turn 60. The reaction may be between -10 ° C and the boiling point of the solvent, preferably take place 10 to 30 ⁰ C. The reaction time is half an hour to several hours.

Optionally, a small amount of toluenesulfonic acid, hydrogen chloride gas or as a catalyst Lewis acids such as boron trifluoride and aluminum chloride can be added.

After the reaction has ended, the solvent can be replaced if necessary. The isolation of the Process product can be done by extracting the reaction mixture with an alkali solution and acidifying the alcoholic layer with hydrochloric acid. The crude product is then with a Solvent extracted or filtered off. This can

NOR ₃

be purified by recrystallization or distillation or by column chromatography.

The chemical structure of the purified compound can be determined by elemental analysis, NMR spectrum or IR spectrum can be determined.

The compounds according to the invention can exist in the following three tautomeric forms;

N —O — R,

Should the compound obtained be converted into a salt are, the process product is mixed with sodium or potassium hydroxide in the presence of a organic solvents such as acetone, methanol, ethanol or dimethylformamide and heated if necessary; you then get the sodium or potassium salt, which is then optionally by reaction with a other metal salt can be converted into the other salt in question. The salts separate often from the solvent used.

The identification of such metal salts, which partially or completely decompose at higher temperatures, can be carried out by means of the infrared absorption spectrum. The not yet purified compound according to the invention shows carbonyl group ^{absorption at a wavelength of 1720 to 1730 cm-1} , while the corresponding metal salt shows the absorption on the side of the longer wavelengths. Optionally, an anion such as OH - can be coordinated with the metal atom of the metal salt at the same time.

The compounds of the invention can be in the form of a corresponding agent before emergence The seeds can be applied directly to or in the soil, or they can be applied to the leaves become or be intimately mixed with the earth. The quantities used are between 50 and 1000 g / Ar, preferably between 100 and 500 g / Ar and in particular between 200 and 300 g / are.

For this purpose, liquid or solid preparations are one or more of the compounds according to the invention contained as an active ingredient, suitable.

The active ingredient in question can be mixed with inert carriers in a conventional manner, for. B. in a mesh powder emulsifiable concentrate, a dusting agent, a granulate, a water-soluble powder or an aerosol be transferred. Suitable solid carriers are bentonite, diatomaceous earth, apatite, gypsum, talc, pyrophyl-Ht, Vermiculite, clay. Suitable liquid carrier materials are kerosene, mineral oil, petroleum, solvent naphtha, Benzene, xylene, cyclohexane, cyclohexanone, dimethylformamide, alcohol, acetone. Possibly a surface-active agent can be added to obtain a homogeneous and stable preparation.

Other customary chemicals can also be added to the compounds according to the invention, as far as they are compatible with it, such as plant nutrients and fertilizers.

The concentration of the active ingredient can be very different and is, for. B. 5 to 80 wt .-%, preferably 20 to 80% by weight, preferably 20 to 80% by weight in the case of wettable powders, 5 to 70 and preferably 10 to

NOR ₃

50 % by weight for emulsifiable concentrates and 0.5 bi; 20, preferably 1 to 10% by weight for dusts.

Mesh powder or emulsifiable concentrates are diluted with water and used as liquid suspensions or Emulsions for the treatment of the soil and foliage: used. Dust can also be added immediately Soil or leaf treatment can be used.

Such preparations are in Examples 11 bi; 16 specified.

example 1

3- [1- (N-allyloxyamino) propylidene] -6-methyl-3,4-dihydro-2H-pyran-2,4-dione

1.8 g (0.01 mol) of 4-hydroxy-6-methyl-3-propionyl-a-pyrone were dissolved in 10 cm ^{3 of} ethanol, whereupon 0.8 g (0.011 mol) of allyloxyamine were added to the solution and these two Hours at Raumtemperatui was stirred. Stirring was then continued at about 70 to 80 ° C. for 30 minutes, the ethanol was then distilled off under reduced pressure and the residue was dissolved in chloroform. The chloroform solution was extracted twice with 7 to 8 cm ^{3 of} 5% sodium hydroxide solution * each time and the alkaline extract obtained was acidified with hydrochloric acid, whereupon an oil separated. The oil was extracted twice with 10 cm of chloroform each time and the chloroform layer was washed with water and then dried with magnesium sulfa. The chloroform was then distilled off under reduced pressure and this gave al: residue 2 g of 3- [1- (N-allyloxyamino) propylidene] -6 methyl-3,4-dihydro-2H-pyran-2,4-dione as colorless ö of the refractive index: η 'S 1.5311.

The yield was 84% of theory.
Weight analysis in% for Ci ₂ Hi ₅ NO ₄ :

Found: C 60.70, H 6.35, N 5.96;
Calculated: C 60.75, H 6.37, N 5.90.

Example 2

3- [1- (N-AHyloxyamino) butylidene] -6-methyl-3,4-dihydro-2H-pyran-2,4-dione

3.0 g (0.015 mol) 3-butyryl-4-hydroxy-6-methyl - «- pyrone were dissolved in 20 cm ^{3 of} ethanol, whereupon 1.2% (0.017 mol) allyloxyamine were added; The solution turned first stirred at room temperature for 2 Stunder and then at 70 to 8O ⁰ C for 30 min then allowed to cool and was then since. Ethanol was distilled off under reduced pressure and the residue was dissolved in chloroform. The chloroform solution

airde extracted twice with 15 cm ^{3 of} 5% sodium hydroxide solution each time. The chloroform layer was washed with water and dried with magnesium sulfate. The chloroform was distilled off and the residue was recrystallized with i-hexane. 2.8 g of 3- [1- (N-AIIyI-oxyamino) -butylidene] -6-methyl-3,4-dihydro-2H-pyan-2,4-dione were obtained as colorless crystals.

Yield was 74%; F. 52 to 54 ° C.

Weight analysis in% for C13H17NO4:

Found: C 62.10, H 6.83, N 5.61;
Calculated: C 62.14, H 6.82, N 5.57.

Example 3

3- [1- (N-Ethoxyamino) propylidene] -6-ethyl-3,4-dihydron-2H-pyran-2,4-dione

2.0 g (0.01 mol) δ-ethyl - ^ - hydroxy-S-propionyl-ix-pyrone and 0.66 g (0.11 mol) of ethoxyamine were reacted and worked up as described in Example 2. 2.0 g of 3- [1- (N-ethoxyamino) propylidene] -6-ethyl-3,4-dihydro-2H-pyran-2,4-dione were obtained as colorless crystals with a melting point of 54 to 55 ° C. The yield was 83.0%.

Weight analysis in% for C12H17NO4:

Found: C 60.19, H 7.10, N 5.90;
Calculated: C 60.25, H 7.11, N 5.86.

Example 4

3- [1- (N-Ethoxyamino) butylidene] -6-propyl-3,4-dihydro-2H-pyran-2,4-dione

2.2 g (0.01 mole) of 3-butyryl-4-hydroxy-6-propyl - «- pyrone and 0.66 g (0.011 mol) of ethoxyamine were reacted and worked up according to Example 1. There were 2.5 g 3- [l-Ethoxyamino) butylidene] -6-propyl-3,4-dihydro-2H-pyran-2,4-dione as a yellowish oil with the refractive index π "οΜ, δ 168 obtained. The yield was 94% of the Theory.

Weight analysis in% for Ci ₄ H ₂ iNO4:

Found: C 62.87, H 7.90, N 5.31;
Calculated: C 62.90, H 7.92, N 5.24.

Example 5

5-Bromo-3- [1- (N-ethoxyamino) propylidene] -6-ethyl-3,4-dihydro-2H-pyran-2,4-dione

1.4 g of 5-bromo-6-ethyl-4-hydroxy-3-propionyl-xpyron (melting point 76.5 ° C.-77.5 ° C.) were dissolved in 10 cm ^{3 of} ethanol, whereupon 0.5 g of ethoxyamine was added and the solution was stirred for 4 hours at room temperature and then for a further 30 minutes at 40 to 50 ° C. After distilling off the ethanol under reduced pressure, white crude crystals that melt after recrystallisation from η-hexane at 46 to 47 ⁰ C received. The yield was 1.3 g (81%).

Example 6

5-Bromo-3- [1- (N-Allyloxyamino) butylidene] ·
6-propyl-3,4-dihydro-2H-pyran-2,4-dione

1.5 g of 5-bromo-3-butyl-4-hydroxy-6-propyl - «- pyrone ( ^{mp 50-51" C) were dissolved in 10 cm 3 of} ethanol, whereupon 0.6 g of allyloxyamine was added and the solution was stirred for 4 hours at room temperature and then for a further 30 minutes at 40 to 50 ° C. After the ethanol had been distilled off under reduced pressure, a colorless viscous liquid remained which was dissolved in 10 cm ^{3 of} ether 20 cm ^{3 of} 5% sodium hydroxide solution extracted and the extract acidified with concentrated hydrochloric acid while cooling. An oil separated, which was separated and ^{extracted twice with 10 cm 3 of} ether. The ether extract was washed with water and dried with magnesium sulfate, whereupon the ether was distilled off under reduced pressure, giving 5-bromo-3- [1- (N-allyloxyamino) butylidene] -6-propyl-3,4dihydro-2H-pyran-2,4-dione as a pale yellowish oil the refractive index η SM, 5535. The yield was 1.6 g (93%).

Example 7

⁵ Sodium salt of 3- (1 -N-allyloxynminobutylidene) -6-methyl-3,4-dihydro-2H-pyran-2,4-dione

2.5 g of 3- (1N-allyloxyaminobutylidene) -6-methyl-3,4-dihydro-2H-pyran-2,4-dione obtained according to Example) 2 were dissolved in 20 cm ^{3 of} acetone, whereupon a solution of 0.4 g of sodium hydroxide in 2 cm ^{3 of} water was gradually added with stirring at room temperature.

The thereby precipitated sodium salt was filtered off. 2.7 g (100%) of the salt as white crystals, melting at 114 to 116 ⁰ G: infrared spectrum 1660 - '(C = O).

Example 8

Nickel salt of 3- (1-N-Ethoxyaiminopropylidene) -6-methyl-3,4-dihydro-2H-pyran-2,4-dione

The starting compound 3- (1-N-ethoxyaminopropylidene) -6-methyl-3,4-dihydro-2H-pyran-2,4-dione was analogous to Example 3 by reacting 0.1 mol of 6-methyl-4-hydroxy-3-propionyl - «- pyrone and 0.011 Moles of ethoxyamine produced.

2.3 g of the reaction product were dissolved in 20 cm ^{3 of} acetone and mixed with a solution of 0.4 g of sodium hydroxide in 2 cm ^{3 of} water while stirring. Stirring was continued for a further 10 minutes, after which a solution of 1.2 g of nickel chloride (NiCl ₂ · 6H ₂ O) in 2 cm of water was added to the reaction mixture with stirring. Then the nickel salt precipitated in the form of green crystals. The yield was 2.4 g (95%). Mp 218-119 ° C (with decomposition); Infrared spectrum (C = O) 1683 cm- '.

Example 9

Copper (H) salt of

3- (1-N-Ethoxyaminopropylidene) -6-ethyl-3,4-dihydro-2H-pyran-2,4-dione

According to Example 8, 2.4 g of the 3- (l -N-ethoxyaminopropylidene) -6-ethyl-3,4-dihydro-2H-pyran-2,4-dione obtained according to Example 3 was first mixed with 0.4 g of sodium hydroxide and then treated with 1.25 g Kupfersulf al (O1SO4 · 5 H ₂ O) was reacted to give the Kupf "r (n) salt in question in the form of green crystals. The yield was 2.7 g (100%), the compound schmoh at 172 to 174 ° C. with decomposition; Infrared spectrum 1673 cm - '(C = O).

Example 10

Barium salt of 3- (l-N-Ethoxyaminopropylidene) -6-ethyl-3,4-dihydro-2H-pyran-2,4-dione

Analogously to example 1, 2!, 4 g of the according to example obtained 3- (1 -N-ethoxyaminopropylidene) -6-ethyl-3,4

Lihydro-2H-pyran-2,4-dione, 0.4 g of sodium hydroxide and 1.2 g of barium chloride (BaCl ₂ · 2H ₂ O) crude crystals of the barium salt in question were obtained. The crude crystals were dissolved in 99.5% ethanol and the insolubles were filtered off. 2.8 g of the barium salt were obtained as a white crystalline powder with a temperature above 300 ^° C.

Infrared spectrum 1673 cm- '(C = O). The yield was 90%.

In Table 1 below there are further inventive Connections compiled by io

which the compounds 6,12,14, Ib, 17,18,20,21,23,2 < 25, 26, 27 and 28 according to Example 1 and the connections 1, 3, 5, 7, 8, 9, 10, 13, 15 and 19 according to the example. The connection 29 according to Example 5, the compounds 30 to 34 according to Example ι the compound 49 according to Example 7 and the compound gen 36, 38, 39, 40, 41, 43 to 47, 48 and 50 according to Example 8.

In Figs. 1 to 25, the infrared spectra are einigi these connections are shown.

Table I.

Chemical name F. in ⁰ C l.-R. am or. Spectr manure Refr.- Fig. No. index No.

1 3- (1-N-Ethoxyaminopropylidene) -6-methyl-3,4-dihydro-2H-pyran-2,4-dione F. 57-58 1

2 3- (IN-Allyloxyaminopropylidene) -6-methyl-3,4-dihydro-2H-pyran-2,4-dione η "1.5720 2

3 3- (1-N-Ethoxyarninobutylidene) -6-methyl-3,4-dihydro-2H-pyran-2,4-dione F. 38-40 3

4 3- (1-N-Allyloxyaminobutylidene) -6-methyl-3,4-dihydro-2H-pyran-2,4-dione F. 52-54 4

5 3- (1-N-Ethoxyarninopentylidene) -6-methyl-3,4-dihydro-2H-pyran-2,4-dione F. 36-38

6 3- (IN-Allyloxyarninopentyliden) -6-methyl-3,4-dihydro-2H-pyran-2,4-dione n'V 1.5299

7 3- (1-N-Ethoxyamino-2,2-dimethylpropylidene) -6-methyl-3,4-dihydro-2H-pyran-2,4-dione m.p. 177-178

8 3- (1 -N-Allyloxyamino-2,2-dimethylpropylidene) -6-methyl-3,4-dihydro-2H-pyran-2,4-dione F. 127-129

9 3- (1-N-AllyloxyaminoethyIiden) -6-ethyl-3,4-dihydro-2H-pyran-2,4-dione F. 39.5-40

10 3- (1-N-Methoxyaminopropylidene) -6-ethyl-3,4-dihydro-2H-pyran-2,4-dione F. 43-44

11 3- (1-N-Ethoxyaminopropyidene) -6-ethyl-3,4-dihydro-2H-pyran-2,4-dione F. 54-55

12 3- (IN-Propoxyaminopropylidene) -6-ethyl-3,4-dihydro-2H-pyran-2,4-dione η " 1.5315 5

13 3- (1-N-Isopropoxyaminopropylidene) -6-ethyi-3,4-dihydro-2H-pyran-2,4-dione F. 44-46

14 3- (IN-Allyloxyaminopropylidene) -6-ethyl-3,4-dihydro-2H-pyran-2,4-dione π 1 ⁵ 1.5389 6

15 3- (1-N-Propargyloxyaminopropylidene) -6-ethyl-3,4-dihydro-2H-pyran-2,4-dione F. 84-86

16 3- (INn-Butoxyaminopropylid'en) -6-ethyl-3,4-dihydro-2H-pyran-2,4-dione η '"' 1.5169

17 3- (1-N-Ethoxyaminobutylidene) -6-ethyl-3,4-dihydro-2H-pyran-2,4-dione η £ 1.5199 7

18 3- (IN-Allyloxyaminobutylidene) -6-ethyl-3,4-dihydro-2H-pyran-2,4-dione π £ 1.5310

19 3- (1-N-Ethoxyaminoethylidene) -6-n-propyl-3,4-dihydro-2H-pyran-2,4-dione F. 57-58 8

20 3- (1-N-Ethoxyaminopropylidene) -6-n-propyl-3,4-dihydro-2H-pyran-2,4-dione π '"1.5265 9

21 3- (IN-Allyloxyaminopropylidene) -6-n-propyl-3,4-dihydro-2H-pyran-2,4-dione η Τ 1.5330 10

22 3- (lN-Ethoxyaminobutylidene) -6-n-propyl-3,4-dihydro-2H-pyran-2,4-dione η Τ 1.5168 11

23 3- (lN-Allyloxyaminobutyliden) -6-n-propyl-3,4-dihydro-2H-pyran-2,4-dione η "ο 1.5300 12

24 3- (IN-AUyloxyaminopropylidene) -6-i-propyl-3,4-dihydro-2H-pyran-2,4-dione η "1.5360 13

25 3- (l-N-Ethoxyamtnopentylidene) -6-n-butyl-3,4-dihydro-2H-pyran-2,4-dione π "1.5148 14

26 3- (lN-Äthoxyaminopropylidt; n) -6-i-butyl-3,4-dihydro-2H-pyran-2,4-dione η Ψ 1.5259 15

27 3- (IN-Allyloxyaminopropylidene) -6-i-butyl-3,4-dihydro-2H-pyran-2,4-dione η "/1.5328 16

28 3- (l-N-Ethoxyamino-3-methylbutylidene) -6-i-butyl-3,4-dihydro-2H-pyran-2,4-dione πΌ ° 1.5173

29 3- (1-N-Allyloxyaminopropylidene) -5-bromo-6-methyl-3,4-dihydro-2H-pyran-2,4-dione F. 47-47.5

30 3- (IN-Ethoxyaminobutyiiden) -5-bromo-6-methyl-3,4-dihydro-2H-pyran-2,4-dione η " 1.5439

31 3- (IN-Allyloxyaminobutylidene) -5-bromo-6-methyl-3,4-dihydro-2H-pyran-2,4-dione η " 1.5512 17

32 3- (1-N-Ethoxyaminopropylidene) -5-bromo-6-ethyl-3,4-dihydro-2H-pyran-2,4-dione F. 46-47 18

33 3- (IN-AHyloxyaminopropylidene) -5-bromo-6-ethyl-3,4-dihydro-2H-pyran-2,4-dione η ² V 1.5690

34 3- (1-N-Ethoxyaminobutylidene) -5-bromo-6-n-propyl-3,4-dihydro-2H-pyran-2,4-dione π "1.5488

35 3- (IN-Allyloxyaminobutylidene) -5-bromo-6-n-propyl-3,4-dihydro-2H-pyran-2,4-dione η ο "1.5535 19

36 Nickel salt of 3- (1-N-Ethoxyaminopropylidene) -6-methyl-3,4-dihydro-2H-pyran-2,4-dione F. 218-219

(Decomp.)

37 Sodium salt of 3- (1-N-allyloxyaminobutylidene) -6-methyl-3,4-dihydro-2H-pyran- F. 114-116 2,4-dione

38 Nickel salt of 3- (1-N-allyloxyaminobutylidene) -6-methyl-3,4-dihydro-2H-pyran- F. 217-218 2,4-dione (decomp.)

39 Copper (II) salt of 3- (1-N-allyloxyaminobutylidene) -6-methyl-3,4-dihydro-2H-pyran- F. 138-139 2,4-dione

40 zinc monobydroxide salt of 3 - (! - N-allyloxyaminobutylidene) -6-methyl-3,4-dihydro- F. from 300 2H-pyran-2,4-dione

41 Calcium salt of 3- (l-N-Ethoxyaminopropylidene) -6-ethyl-3,4-dihydro-2H-pyran-2,4-dione F. from 300 20

42 Barium salt of 3- (l-N-Ethoxyaminopropylidene) -6-ethyl-3,4-dihydro-2H-pyran-2,4-dione F. from 300 21

43 Manganese (II) salt of 3- (l-N-Ethoxyaminopropylidene) -6-ethyl-3,4-dihydro-2H-pyran- F. from 300 2.4-dione

22nd

continuation

Chemical name binding No.

F. in ° C 1.-R.

or speculation

Ref.- Fig.

Index no.

44 Iron (III) salt of 3- (1-N-Ethoxyaminopropylidene-6-ethyl-3,4-dihydro-2H-pyran-2,4-dione

45 Cobalt salt of 3- (1-N-Ethoxyaminopropylidene) -6-ethyl-3,4-dihydro-2H-pyran-2,4-dione

46 Nickel salt of 3- (1-N-Äthoxyaminopropyiiden) -6-ethyl-3,4-dihydro-2H-pyran-2,4-dione

47 Copper (II) salt of 3- (1-N-Ethoxyaminopropylidene) -6-ethyl-3,4-dihydro-2H-pyran-2,4-dione

48 Silver salt of 3- (1-N-Ethoxyaminopropylidene) -6-ethyl-3,4-dihydro-2H-pyran-2,4-dione

49 Sodium salt of 3- (1-N-isopropoxyaminopropylidene) -6-ethyI-3,4-dihydro-2H-pyran-2,4-dione

50 Calcium salt of 3- (1-N-allyloxyaminopropylidene) -6-ethyl-3,4-dihydro-2H-pyran-2,4-dione

51 Copper (II) salt of 3- (1-N-ethoxyaminobutylidene) -6-propyl-3,4-dihydro-2H-pyran-2,4-dione

F. 144-14522

(Decomp.)

F. 218-21923

(Decomp.) '

F. 223-224

(Decomp.)

F. 172-17424

(Decomp.)

F. 132-135

(Decomp.)

F. 125-128

(Decomp.)

F. from 300 25

F. 151-152

Example 11 Wettable powder Parts by weight ° Example 14 Parts by weight Compound 1 (Table I)
Diatomaceous earth
Sodium alkyl sulfate
Talk 50
21
9
20th Emulsifiable concentrate 50
30th
12th
8th Compound 4 (Table I)
30 xylene
Dimethylformamide
Polyoxyethylene phenyl ether

The above ingredients are mixed homogeneously and finely ground. A wettable powder is obtained with 50% active ingredient. When used, it is diluted with water to a certain concentration and used as a Sprayed suspension.

Example 12 The mixture containing 50% active ingredient is zi

processed an emulsifiable concentrate, which be diluted accordingly with water unc is sprayed as an emulsion.

Example 15

Dust

Wettable powder

Compound 2 (Table I)
Diatomaceous earth
Sodium alkyl sulfate
Talk

Parts by weight

30th

35

26 Compound 5 (Table I)
Talk
Bentonite
volume

Sodium alkyl sulfate

Parts by weight 10 38 10 37 5

A homogeneous mixture is prepared and finely ground; the agent then contains 30% active ingredient and is diluted with water to a certain concentration and sprayed as a suspension.

Example 13 Emulsifiable Concentrate

The components are mixed homogeneously and finely chopped up. The fine particles become too a granulate with a grain size of 0.5 to 1.0 mm.

The Stüubmittcl containing 10% active ingredient is applied immediately upon application.

Gcw.-Tcilc 25 50 13 12

Compound 3 (Table I)
Xylene

Dimethylformamide
Polyoxyethylene phenyl ether

After mixing and diluting the ingredients, you get an emulsifiable concentrate with 25% Active ingredient. When using it, it is diluted with water and sprayed as an emulsion.

_{5 <i} example 16 Gcw.-Partc Stüubmittcl 3 85 Compound 6 (Table I) 9 Talk 1 do bentonite 2 Carboxymethyl cellulose Sodium alkyl sulfate

The components are first finely chopped up

f> 5 and from the mixture then a granulate in one

Grain size of 0.5 to I ₁ O mm prepared containing 3% active ingredient. The granulate is applied immediately as a dusting agent.

For this purpose 10 sheets of drawings

Claims (3)

Patent claims: 1. 3,4-Dihydro-2H-pyran-2,4-diones of the general a formula NH - O - R ·, in which Ri and R _{2 are} alkyl groups with 1 to 4 carbon atoms, R _{3 is} an alkyl group with 1 to 4 carbon atoms, an allyl or propargyl group and X is a hydrogen or bromine atom, but Ri and R _{2 are} not both a methyl group at the same time , as well as their metal salts. 2. 3- [1- (N-Ethoxyamino) propylidene] -6-ethyl-3,4-dihydro-2H-pyran-2,4-dione. 3. Use of the dihydropyran-2,4-diones according to claim 1 or 2 as herbicides or plant growth regulators.