DE2204738A1 - Herbicidal compounds and agents - Google Patents

Description

The present invention relates to substituted octahydropyrindenes, Process for their preparation, as well as s.elective herbicidal compositions which have such substituted octahydropyrindenes as active ingredients contain and method for combating weeds and grass weeds using the new active ingredients or equivalent means.

The term "octahydropyrindenes" is used here and in the following for substituted 2-azabicyclo [4. 3.0] -decane (octahydro-1-pyrindenes) second hand.

The new substituted octahydropyrindenes correspond to the form L I:

^R L

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Agrlpaf S.A.

In this formula mean

R an optionally halogen-substituted alkyl radical having 1 to 4 carbon atoms, .an optionally halogen-substituted alkenyl radical having 3 to 4 carbon atoms, R, and
Ry each hydrogen or one methyl and the other

Hydrogen and
X oxygen or sulfur.

Possible alkyl radicals R are straight-chain or branched radicals, i.e. methyl, ethyl, n-propyl, isopropyl, η-butyl, sec-butyl, tert-butyl radical. The alkenyl residues R include allyl, 2-butenyl, 3-butenyl and the methylallyl radical. The term halogen is intended to be chlorine and Include bromine.

As halogen-substituted alkyl and alkenyl radicals with a maximum of 4 carbon atoms are the

2-chloroethyl, 3-chloro-n-propyL-, 2-ChloralLyL- and 3-chloroallyl radicals preferred.

Compounds of the formula I, in which X is oxygen, have a particularly favorable selection of these have those compounds in which R is an alkyl radical with L to 4 carbon atoms, the 2-ü \ LoräthyL-, 3-chloropropyl or the ALLyLrest darateL Lt :, particularly good herbicides Properties.

The substituted octahydropvrindenes of Form I. get wet; Obtained by making an octahydropyrind ch'.r formula [Γ

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(ID

either with a thiocarbonic acid halide of the formula III

Hal -C-S-R (III)

It

or with the formation components of such a halide, viz Phosgene or thiophosgene and the alkali metal salt of a mercaptan of the formula IV

R-SH (IV)

reacted in the presence of an acid-binding agent. In formulas II to IV, R, R, and R _? the meanings given under formula I, Hal in formula III represents chlorine or bromine. It is advisable to carry out the reactions in a solvent and / or diluent which is inert towards the reactants. The type of distribution agent to be used is largely determined by the acid-binding agent used in the reaction. If organic bases such as tertiary amines are used, it is advisable to also use organic solvents. In the case of inorganic bases, water and aqueous mixtures of water-miscible organic solvents are suitable. In general, the following tertiary amines can serve as acid-binding agents: pyridine and pyridine bases, triethylamine, triethylene = etc .; likewise, the respective octahydropyrindene of the formula II, used in excess in the reaction, can be used as an acidic

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serve as a binding agent. The hydroxides and carbonates of the alkali and alkaline earth metals come from inorganic bases, primarily sodium hydroxide, sodium carbonate, potassium carbonate, also the hydroxides and carbonates of lithium, Barium, strontium, magnesium and quaternary ammonium compounds that act as bases in the presence of water react, for example tetramethylammonium hydroxide, etc., into consideration.

The following solvents can be used: aliphatic and aromatic hydrocarbons and halogenated hydrocarbons, such as benzene, toluene, xylenes, petroleum ether, chlorobenzene, methylene chloride, chloroform, carbon tetrachloride, ether and ethereal solvents such as dialkyl ethers, tetrahydrofuran; as water-miscible solvents are: alkanols, ketones, etc.

When implementing a Cctahydropyrinders the Jarmel II with phosgene or thiophosgene and an alkali metal salt of a mercaptan can be obtained as an intermediate Octahydropyrindene-1-carbonyl halide without further purification be reacted with an alkali metal salt of a mercaptan of the formula IV.

For the preparation of the new substituted octahydropyrindenes of the formula I, in which X is oxygen, a process is preferred in which one uses an octahydropyrindene of the formula II in the presence of an acid-binding agent with carbon oxysulfide (COS) and then with an alkylating agent or alkenylating agent. The bases listed above are used as acid-binding agents, preferably alkali metal hydroxides. The alkylating agents are primarily alkyl halides and also dialkyl sulfuric acid esters and alkyl esters of toluenesulfonic acids are suitable, as alkenylating agents especially alkenyl halides and alkenyl tosylates.

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Agripat S.A.

For the preparation of substituted octahydropyrindenes of the formula I, in which X is sulfur, a similar process variant is preferred: an octahydropyrindene of the formula II is in the presence of an inorganic or organic base with carbon disulfide and then reacted with an alkylating agent or alkenylating agent.

The novel reactions of a substituted Octahydropyrindens of formula II as described for compounds of the formula are carried out at temperatures of -20 to + 10O ⁰ C, preferably between 0 and +30 ⁰ C III.

The octahydropyrindenes of the formula II are known compounds [see H.L. Lochte and A.G. Pittmann in J. At the. Chem. Soc. 82,469 (1960)].

The new substituted octahydropyrindenes of the Formula I have excellent herbicidal and plant regulatory properties, some of them also fungicidal properties. The herbicidally active derivatives are partly used as general herbicides and partly for combating weeds and grass weeds in cereals including maize, also in soy, cotton, sugar beet and rice crops (water and dry rice cultures).

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These active ingredients include weed types that are difficult to control in rice crops: for example, in water rice crops Echinochloa sp., Eleocharis sp., Monochoria, Sagittaria. , Panicum sp. , Cyperaceae, Rotala, Lindemia, Vandellia, Paspalum sp. , Etc.; in dry rice cultures also Echinochloa sp., Digitaria sp., Brachiaria sp., Sida sp., Cyperaceae, Acanthosperum sp. etc .. As the active ingredients gradually kill the unwanted plants and thus the oxygen balance and the biological equilibrium are not grossly impaired, they are for the application very suitable in water rice crops. In addition, the active ingredients have a broad spectrum of action against various types Aquatic weeds, e.g. against emersed plants, aquatic plants with and without floating leaves, submerged Plants, algae etc.

The wide range of effects of the new substituted Octahydropyrindenes of the formula I also allow them to be used for the important control of weeds and grass weeds in the area surrounding the crops, such as ditches, canal beds, dams, etc. Of these active ingredients are not only the grass weeds mentioned, which occur in useful plant crops, but also other grass-like and broad-leaved weeds destroyed. The active ingredients can be used in the preparation of the acreage and after emergence of the cultivated plants are used to destroy an already accrued weed population. The application rates are different and depend on the time of application, they are between 0.25 and 6, preferably 0.5 and 2 kg Active ingredient per hectare, when applied before the plants emerge. Application rates of 10 to 30 kg of active ingredient per Hectares can be used for a total destruction of the entire weed population, for example on neighboring cultivated land Wasteland, are applied.

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Agripat S.A.

In addition, such substituted octahydropyrindenes can also be used as growth regulators, for example can be used for defoliation, delaying flowering, etc. With the new connections the vegetative becomes Plant growth and the ability to germinate influences the formation of flowers, fruit development and training encouraged by separation tissues. The formation of undesirable stinging instincts in various types of plants becomes very great greatly diminished. The new compounds also have a secretion-promoting effect, e.g. the latex flow in Hevea brasiliensis promoted. As experiments have shown, the rooting of seedlings and cuttings, as well as the formation of tubers positively influenced by potatoes. The germinability of seeds, such as seed potatoes and legumes, is promoted at lower concentrations and prevented at higher concentrations. Both the one and the other effect are of economic importance. In the case of many ornamental and cultivated plants, the flowering date and the number of flowers must be controlled Flowers possible. If all bushes bloom at the same time, the bushes can be harvested within one comparatively short time.

Tests also showed that fruit trees thinned out blossoms and fruit. Continue to be e.g. in apples, pears, peaches, tomatoes, bananas and pineapples accelerates fruit ripening and coloration and improved. Through the formation of separation tissue the fruit and leaf abscission is made much easier. This is of great economic importance for the mechanical Harvest, e.g. of citrus fruits or cotton.

Substituted octahydropyrindenes of formula I are has not yet been described. In the American patent specification No. 3,344,134 herbicidal azabicyclo- [3.2.2.] - nonanthiolcarbamates described, their effect on grass weeds is, however, with good selectivity in cultivated

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Plant sparsely and dicotyledonous weeds are not harmed. The inventive active ingredients of Formula I show a much better effectiveness against grass weeds and have a broader spectrum of action dicotyledonous weeds. Some are well tolerated by grain, especially corn and Wheat, also soy, sugar beet and cotton, even with very low application rates, against a multitude of grassy species Weeds herbicidally effective against which the comparison compounds mentioned have no or only inadequate properties Show effects.

Some of the new substituted octahydropyrindenes of the formula I already have low concentrations below the application rates for herbicidal effect, an excellent fungicidal effect on phytopathogenic fungi. For example, powdery mildew fungi such as cucumber powdery mildew (Erysiphe cichoriacearum), apple powdery mildew (Podosphaera leucotricha), rose powdery mildew (Sphaerotheca pannosa), wheat powdery mildew (Erysiphe graminis) and downy mildew, such as the causative agent of late blight of the potato (Phytophthora infestans), the downy mildew of the vine (Plasmophora viticola), also leaf spot pathogens such as the pathogen of the tomato blotch disease (Alternaria solani), leaf spot disease of celery (Septoria spicola) and rust fungi such as bean rust (Uromyces appendiculatus), also the difficult to control gray mold (Botrytis cinerea) etc., killed or killed when the new active ingredients are used inhibited in their growth. In addition to an excellent long-term effect, the compounds also have a good curative effect, as a result of which fungi have already penetrated plant tissue after application of the new compounds killed v / earth.

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To produce herbicidal agents, the active ingredients are mixed with suitable carriers and / or distributors. To broaden the spectrum of activity you can add other herbicides to these agents, for example from the s-triazine series such as 2-halo-4-6-diaminos-s-triazines or 2-alkoxy- or 2-alkylthio-4,6-diamino-s-triazines, from the series of triazoles, diazines such as uracils, aliphatic carboxylic acids or halocarboxylic acids, the halogenated benzoic acids and phenylacetic acids, the phenoxyalkanecarboxylic acids, the Hydrazides, amides such as substituted anilides, nitriles, phenylureas, carbamic acid esters or the thiocarbamic acid ester.

The following examples illustrate the manufacturing processes of the new substituted octahydropyrindenes of the formula I. The temperatures are in degrees Celsius specified.

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example 1

188 g of octahydro-1-pyrindene are dissolved in 1000 ml of diethyl ether and this is covered with a solution of 84 g of potassium hydroxide in 500 ml of water. With vigorous stirring and cooling (5-10 °), 187 g of S-ethyl chlorothioate are added dropwise to the mixture. After the reaction has ended, the mixture is stirred for a further 30 minutes, the phases are then separated, the organic phase is washed neutral with water, The ether is dried and evaporated in vacuo. The remaining oil is distilled in vacuo. 281 g of - (ethylthio-carbonyl) -oetahydro-1-pyrindene are obtained as a colorless oil with a boiling point of 108-112 ° / 0.4 Torr. [Compound No. 1]

Example 2:

If, as described in Example 1, 40.5 g of octahydro 1-pyrinden in 200 ml of petroleum ether and 13 g of sodium hydroxide

in 100 ml of water with 32 g of phosgene with stirring and cooling to -5 ° to 0 °, so obtained after working up the organic Phase the octahydro-l-pyrinden-N-carboxychloride. The implementation of this intermediate in petroleum ether with an aqueous solution of 27 g of sodium ethyl mercaptide yields 55 g after the organic phase has been worked up colorless oil, the physical constants of which agree with those from example 1.

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Example 3:

A solution of 16 g of octahydro-1-pyrindene and 13 g of triethylamine in 200 ml of benzene is added dropwise with stirring and
Cool slowly 17.7 g of chlorothioformic acid sn-propyl ester. After the reaction has ended, the mixture is stirred for a further 3 hours at room temperature, and the reaction solution is separated from the precipitated
Triethylammonium chloride by filtering and the benzene evaporated in vacuo. The resulting yellowish oil is im
Vacuum distilled. 22 g of 1- (n-propylthio-carbonyl) -octahydro-1-pyrindene are obtained as a colorless oil with a boiling point of 100-110 ° / 0.01-0.02 Torr. [Compound No. 2]

Example 4:

In a solution of 25 g of octahydro-1-pyrindene and 8 g of sodium hydroxide in 400 ml of 50% strength aqueous ethanol, 12.2 g of carbon oxysulphide are introduced at 0 ° -5 ° with slow stirring. Half an hour after the end of the reaction
27.5 g of n-butyl bromide are rapidly added dropwise, and the mixture is stirred for 5 hours at 25 ° much more. The alcohol is removed in vacuo and the oil formed is taken up in methylene chloride. After this
Drying and distilling off the solvent, the yellowish oil is distilled in vacuo. 27 g of 1- (τι-butyl thio-carbonyl) -octahydro-1-pyrindene are obtained as a colorless oil with a boiling point of 125-128 ° / 0.1 Torr. [Compound No. 3]

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Example 5:

To a solution of 12.5 g of octahydro-1-pyrinden and 4 g of sodium hydroxide in 150 ml of 50 7 ₀ sodium, aqueous ethanol is added dropwise a solution of 7.6 g of carbon disulfide in 50 ml of ethanol to at 0-5 °. After stirring for one hour at 0-5 °, 8 g of allyl chloride are added to the mixture and stirring is continued for 20 hours at 25 °. It is then diluted with water and the oil which has separated out is extracted with ether. After drying, the ether is evaporated in vacuo and the yellowish oil that remains is dried in a high vacuum C18 κ). The 1- (allylthio-t-hiocarbonyl) -octahydro-

20 1-pyrinden has the refractive index n _ß = 1.6092. [Link

No. 4]

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Agripat S.A.

According to the methods described in these examples, using the appropriate amounts of octahydropyrindene and thiocarbonic acid halide of the formula II or carbon oxysulphide or carbon disulfide and alkenyl The compounds of the formula I listed in Table I below are prepared:

Table I.

Verb.
No. links Melting point,
Boiling point or
Refractive index 5 1- (methylthio-carbonyl) octa
hydro-1-pyrinden 94 ° / 0.1 torr 6th 1- (Isopropylthio-carbonyl) -octa
hydro-1-pyrinden 100 ° / 0.1 torr 7th 1- (see Butylthio-carbonyl) -octa
hydro-1-pyrinden 115-118 ° / 0.5 torr 8th 1-Ctert.Butylthio-carbonyl) -
octahydro-1-pyrinden 110 ° / 0.5 torr 9 1- (2-chloroethylthio-carbonyl) -
octahydro-1-pyrinden 125-135 ° / 0.03 torr 10 1- (3-chloropropylthio-carbonyl) -
octahydro-1-pyrinden 170-180 ° / 0.01
Torr 11 1- (Allylthio-carbonyl) -octa
hydro-1-pyrinden 105-108 ° / 0.05
Torr 12th 1- (Methallylthio-carbonyl) -octa
hydro-1-pyrinden 113-116 ° / O, 03
Torr 13th 1- (ethylthio-carbonyl) -3-methyl-
octahydro-1-pyrinden 94 ° / 0.12 torr 14th 1- (n-propylthio-carbonyl) -3-methyl-
octahydro-1-pyrinden 107 ° / 0.17 torr

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Verb.
No. links Melting point,
Boiling point or
Refractive index 15th 1- (ethylthio-carbonyl) -4-raethyl-
octahydro-1-pyrinden 115-118 / 0.07 torr 16 1- (isopropylthio-carbonyl) -4-
methyl-octahydro-1-pyrindene 96-100 / 0.1 torr 17th 1- (methylthio-thiocarbonyl) -
octahydro-1-pyrinden Mp 44-48 ° 18th 1- (ethylthio-thiocarbonyl) -
octahydro-1-pyrinden 135-145 / 0.005
Torr 19th 1- (isopropylthio-thiocarbonyl) -
octahydro-1-pyrinden n ^ ⁰ = 1.5925 20th 1- (n-butylthio-thiocarbonyl) -
octahydro-1-pyrinden Πρ ⁰ = 1.5842 21st 1- (2-chloroallylthio-thiocarbonyl) -
octahydro-1-pyrinden n ^ ⁰ = 1.6133 22nd l- (3-cis-chlorallylthio-thio-
carbonyl) octahydro-1-pyrindene n ^ ⁰ = 1.6203 23 1- (3-trans-chloroallylthio-thio-
carbonyl) octahydro-1-pyrindene n ^ ⁰ = 1.6205 24 1- (allylthio-thiocarbonyl) -3-
methyl-octahydro-1-pyrindene n ^ ⁰ = 1.5974 25th 1- (allylthio-thiocarbonyl) -4-
methyl-octahydro-1-pyrindene n ^ ⁰ = 1.5988

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The herbicidal action of the new compounds is illustrated by the following experiments.

I. Pre-emergence attempt

The active ingredient is supplied in soil as a 10% powder concentrate at a concentration of 16 kg of active ingredient per hectare incorporated. The soil prepared in this way is poured into seed trays, in which the following test plants are sown became:

Millet (Setaria italica), mustard (Sinapis alba), oats (Avena sativa), ryegrass (Lolium perenne) and vetch (Vicia sativa).

The dishes were then kept under daylight in the greenhouse at 20-24 ° C. and 70 % relative humidity.

The test is evaluated after 20 days and the assessment is based on the 9 index.

9 = plants undamaged = control

1 - plants dead

8-2 = intermediate stages of damage

- = not checked

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Table II

Active ingredient
Connection no. millet
(Setaria
italica) mustard
(Sinapis
alba) oats
(Ave na
sativa) Ryegrass
(LoIium
perenne) Vetch
(Vicia
sativa) 1
2
3
6th
13th
14th 1
1
2
1
1
1
- 2
2
6th
5
3
2
i 1
1
2
1
1
2 1
1
1
1
1
1 2
2

The 10% powder concentrate has the following composition. 10 parts of active ingredient, 0.6 part of sodium dibutylnaphtha linsulphonic acid, 1 part of naphthalenesulphonic acids Phenol sulfonic acid-formaldehyde condensate (3: 2: 1), 10 parts Sodium aluminum silicate and 78.4 parts kaolin.

II. Selective pre-emergence experiment with sown test plants

Immediately after the test plants have been sown in seed trays, the active ingredients are obtained as an aqueous suspension from a 25% wettable powder, applied to the surface of the earth. Then the seed trays are at 22-25 ° C and 50-70% relative humidity under daylight held.

The evaluation is carried out after 28 days according to the 9 index given above.

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Agripat S.A.

The following were sown as test plants:

Crops : Wheat (Triticum vulgar) soy (Glycine max.) cotton (Gossypium hirsutum) Corn (Zea mays) rice (Oryzasativa) Sugar beet (Beta vulgaris) Weeds: Echinochloa crus ealli

^v a) dry b) in water Poa trivialis Alopecurus myosuroides Digitaria sahguinalis Amaranthus spec. LoIium multiflorum Setaria italica

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Act hurry III - selective attempts
Condition of the sown plants after 4 weeks

active substance
No. Κοπζ.
kg / ha Crops soy tree
wool Weeds / grass weeds in Uiasser Poa
trivialis Alopecurus Digitaria Amaranthus -L oil ium Setaria 1 4th
2
1 wheat 7th
7th
7th 6th
7th
9 Echi nochloa
crus galli 1
1
2 1
1
1 2
2
3 1
1
8th 1
3
5 ro ro - ■ 1
2
2 2 4th
2
1 - 8th
8th
8th 4th
9
9 trek 2
2
6th 1
1
3 1
2
7th 2
3
5 2
3
3 «- · - CVJ 2
2
3 3 4th
2
1 8th
8th
9 1 I I 7th
8th
9 1
1
2 2
2
5 1
1
1 2
2
6th 1
2
4th 1
2
4th 1
1
1 1
2
3 9
9
9 1
1
7th 2
2
2

Ni N> O

(Continued) Table III - Selective Attempts

Condition of the sown plants after 4 weeks

ro ο co oo co

Active substance
No. Conc.
kg / ha Crops he
co soy O
Z3
approx
CO Corn water
rice Dry
rice sugar
beets Weeds Echinucl
crus ga
dry ¹ I? ³
in water Hoa
trivialis Alopecia
curus Uigi-
taria Ama-
ranthus Lo I ium üetaria 6th 4th 9 3 7th 8th _ 9 1 1 1 CVl 1 1 1 1 CVJ 9 8th 9 8th - - 9 CVJ 1 1 2 1 3 CvI CVl 1 9 8th 9 9 - - 9 CVl 1 1 6th 2 7th 2 6th 7th ¹ 4 CJl 8th 7th 9 3 3 8th CVI 1 3 CVJ 1 3 4th 1 2 7th 8th 8th 9 6th 8th 8th CVl CVJ 3 3 CVl 3 5 CVl 1 8th 9 9 9 7th 9 8th CVJ 2 4th 6th 7th 4th 8th 4th 10 4th 8th 8th 7th egg 9 9 9 CVJ CVJ 3 - CVI 1 3 2 2 9 9 8th 9 9 9 9 2 CVl 3 - 2 3 3 CVl 1 9 9 9 9 9 9 9 CVJ 2 3 - CVl 3 2 CVJ A. 4th 9 9 9 - - - - 3 1 4th 6th 2 4th 3 3 CVJ 9 9 9 - - - - 6th 7th 8th 6th 3 6th 9 4th ] 9 9 9 - - - - 7th 9 9 9 9 9 9 9

A = 3 - (ethylthio-carbonyl) -3-azabicyclo- [3.2. 2.] -nonan

(known from U.S. Patent No. 3,344,134)

AgripatSA

III. The following experiments show the inhibiting influence on the length growth of various plant species:

A) Application to grasses

A lawn mixture consisting of Lolium perenne (20 7 _O ) , Poa pratensis (23 %), Agrostis tenuis (10 %) and Festuca rubra (47%) is cultivated in seed trays for 4 months and cut once a week. The freshly cut lawn, about 1.5 cm high, is then treated with aqueous or aqueous-acetone solutions. The lawn is then kept at 25 ° and 65% relative humidity below 15,000 lux. The growth in length is rated 4 weeks after application of the active ingredients.

In the following Table IV is the by the active ingredient in Reduction in length growth caused by different application rates according to the following rating key specified:

6 = no effect, like untreated lawn 5 = approx. 15% inhibition of the growth in length 4 = approx. 35% inhibition of the growth in length. 3 = approx. 50% inhibition of longitudinal growth 1 «= maximum inhibition
C «= deeper green coloration of the leaves N = slight marginal necrosis of the leaves

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Table IV Lolium
perenne Poa
pratensis Agrostis
tenuis Festuca
rubra Active ingredient
Verb., No. 4C
4C 4C
4C 4C
4C 4th
4C 1
2 B) Application to cereals

Different types of grain (spring wheat, rye and oats) are cultivated in seed trays. When the plants have reached the 2-leaf stage, they will

a) with an aqueous or aqueous-acetone 0.5% resp. 0.1% active ingredient solution sprayed dripping wet and then in a climatic chamber at 25 °, and & 3% rela- ■ tive humidity kept below 15,000 lux. After 21 days, the growth in length of the plants will decrease determined by measuring the distances between the nodes (internodal distances). · /

t>) with an aqueous or water-acetonic broth Poured in the specified concentration of active ingredient in such a way that the above-ground part of the plant remains untouched. The plants are then grown in the climatic chamber under the above conditions. 4 weeks after Application, the growth in length is determined and rated in the same way as under A).

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Table V

Active ingredient
Verb. No. concentration Spring wheat rye oats 3rd N.
3 CO CO b) Floor application 3
4th CO CO a) Leaf application Ui Ui 2 0.5
0.1 co co 1 0.5
0.1

The other substances were tested in the same way and showed similar effects.

The herbicidal compositions according to the invention are produced by intimately mixing and grinding active ingredients of the general formula I with suitable carriers, optionally with the addition of opposite the Active ingredients, inert dispersants or solvents. The active ingredients can be used in the following working-up forms are available and applied:

solid processing forms: dusts, grit,

Granules, coating granules, impregnation granules and

Homogeneous granules; Active substance concentrates dispersible in water: wettable powder

(wettable powder), pastes, emulsions;

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liquid forms of preparation: solutions

For the production of solid processing forms (dusts, grit, granulates), the active ingredients are used with mixed with the solid carriers. Come as carriers for example kaolin, talc, bolus, loess, chalk, limestone, lime grit, dolomite, diatomaceous earth, precipitated silica, Alkaline earth silicates, sodium and potassium aluminum silicates (feldspars and mica), calcium and magnesium sulfates, ground plastics, fertilizers such as ammonium sulfate, ammonium phosphates, ammonium nitrate, ureas, ground vegetable products such as grain flour, tree bark flour, wood flour, nut shell flour, cellulose powder, residues of plant extractions, activated charcoal, etc., each individually or as mixtures with one another.

The grain size of the carrier materials is expediently up to approx. 0.1 mm for dusts and approx. 0.075 for grit up to 0.2 mm and for granulates 0.2 mm or more.

The active ingredient concentrations in the solid preparation forms are 0.5 to 80%.

These mixtures can also contain additives stabilizing the active substance and / or nonionic, anionic active substances and cation-active substances are added, for example, the adhesive strength of the active ingredients on plants and Improve plant parts (adhesives and adhesives) and / or better wettability (wetting agents) and dispersibility (Dispersants). The following can be used as adhesives, for example: olein-lime mixture, Cellulose derivatives (methyl cellulose); Hydroxyäthylglykoläther of mono- and dialkylphenols with 1 to 15 ethylene oxide residues per molecule with 8-9 carbon

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atoms in the alky Ires t, ligninsulphonic acids, their alkali and Alkaline earth salts, polyethylene glycol ether (Carbowaxe), fatty alcohol polyethylene glycol ether with 5-20 ethylene oxide residues per molecule and 8-18 carbon atoms in the fatty alcohol part, condensation products of ethylene oxide, propylene oxide, polyvinylpyrrolidones, Polyvinyl alcohols, "condensation products of urea-formaldehyde and latex products.

Active substance concentrates which are dispersible in water, ie wettable powders, pastes and emulsion concentrates, are agents which can be diluted with water to any desired concentration. They consist of active ingredient, carrier, optionally additives stabilizing the active ingredient, surface-active substances and antifoam agents and optionally solvents. The active ingredient concentration in these agents is 5 80 %.

The wettable powders and pastes are obtained by mixing the active ingredients with dispersants and powdery carriers in suitable devices mixed and ground until homogeneous. As carrier materials, for example, those above come for the solid Forms of processing mentioned in question. In some cases it is advantageous to use mixtures of different carriers to use. The following can be used as dispersants, for example: condensation products of sulfonated Naphthalene and sulfonated naphthalene derivatives with formaldehyde, condensation products of naphthalene or the Naphthalenesulfonic acids with phenol and formaldehyde as well as alkali, ammonium and alkaline earth salts of ligninsulfonic acid, further alkylarylsulfonates, alkali and alkaline earth metal salts of dibutylnaphthalenesulfonic acid, fatty alcohol sulfates, such as salts of sulfated hexadecanols, heptadeca-

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nols, octadecanols and salts of sulfated fatty alcohol glycol ethers, the sodium salt of oleyl ethionate, the sodium salt of oleyl methyl tauride, ditertiary acetylene glycols, Dialkyldilaurylammonium chloride and fatty acid alkali and alkaline earth salts.

Silicones, for example, can be used as antifoam agents.

The active ingredients are mixed, ground, sieved and passed with the additives listed above in such a way that in the case of wettable powders, the solid fraction does not exceed a particle size of 0.02 to 0.04 mm and in the case of pastes it does not exceed 0.03 mm. Zui? Preparation of emulsion concentrates and pastes will use dispersants as described in the preceding Sections were listed, organic solvents and water used. Examples of solvents are used the following in question: alcohols, benzene, xylenes, toluene, dimethyl sulfoxide and in the range of 120 35O ° C boiling mineral oil fractions. The solvents must be practically odorless, not phytotoxic, the active ingredients be inert to and not easily flammable.

The agents according to the invention can also be in the form of of solutions can be applied. For this purpose, the active ingredient or several active ingredients of the general formula I are used in suitable organic solvents, solvent mixtures or water. As an organic solvent Aliphatic and aromatic hydrocarbons, their chlorinated derivatives, alkyl naphthalenes, mineral oils alone can be used or used as a mixture with one another. The solutions should contain the active ingredients in a concentration range of 1 to 20%.

209834/1219

Agripat S.A.

Leave the described agents according to the invention other biocidal active ingredients or agents are mixed in. So the new means can in addition to the compounds mentioned of the formula I, for example, insecticides, fungicides, bactericides, fungistats, bacteriostats or nematocides for Broadening the spectrum of activity included. The invention Agents can also contain plant ingredients, trace elements, etc.

Work-up forms of the new substituted octahydropyrindenes are described below. Parts mean Parts by weight.

granules

The following substances are used to produce 5% granules:

5 parts of an active substance of the formula I,

0.25 part of epichlorohydrin,

0.25 part of cetyl polyglycol ether

3.50 parts of polyethylene glycol ether (Carbowax),

91 parts of kaolin (grain size 0.3-0.8 mm).

The active substance is mixed with epichlorohydrin and dissolved in 6 parts of acetone, then polyethylene glycol ether is added and cetyl polyglycol ether added. The solution obtained in this way is sprayed onto kaolin and the solvent then evaporated in vacuo.

Wettable powder

To produce a) 70%, b) 25% and c) 10% wettable powder, the following ingredients are used:

209834/1219

Agripat SA. j -

-yr-

a) 70 parts of an active substance of the formula; Γ.

5 parts of sodium dibutyl naphthyl sulfonate,

3 parts of naphthalenesulfonic acids-phenaolsulfonic acids-formaldehyde condensate 3: 2: 1,

10 parts kaolin,

12 parts of champagne chalk;

b) 25 parts of an active substance of the formula I.

5 parts of oleyl methyl tauride sodium salt,

2.5 parts of naphthalenesulfonic acid-formaldehyde condensate,

0.5 parts of carboxymethyl cellulose, 5 parts of neutral potassium aluminum silicate, 62 parts of kaolin;

c) 10 parts of an active substance of the formula I.

3 parts mixture of the sodium salts of saturated fatty alcohol sulfates,

5 parts of naphtahlinsulfonic acid-formaldehyde condensate,

82 parts of kaolin.

The specified active ingredient is applied to the appropriate carriers (kaolin and chalk) and then mixed and wedded. Spray powder is obtained from excellent wettability and floating ability. From such Wettable powders can be diluted with water to obtain suspensions of any desired active ingredient concentration will.

209834/1219

Agripat S.A.

paste

The following are used to produce a 45% paste Substances used:

Parts of an active ingredient of the formula I.

5 parts sodium aluminum silicate,

Parts of cetyl polyglycol ether with 8 moles of ethylene oxide,

1 part oleyl polyglycol ether with 5 mol

Ethylene oxide,

2 parts spindle oil,

Parts of polyethylene glycol, . 23 parts of water.

The active ingredient is intimately mixed and ground with the additives in suitable equipment. You get a paste that can be diluted with water to produce suspensions of any desired concentration.

Emulsion concentrate

For the production of a 10% emulsion concentrate

209834/1210

Agripat S.A.

will

10 parts of an active ingredient of the formula I 15 parts of oleyl polyglycol ether with 8 moles

Ethylene oxide, 75 parts isophorone

mixed together. This concentrate can be diluted with water to form 0.1% emulsions, for example. Such emulsions are used, for example, before the emergence of corn, soy, cotton, wheat, dry rice, oats, Barley, rye, sugar beet, potatoes and other crops applied.

209834/1219

Claims (25)

Claims R is an alkyl radical with 1 to 4 carbon atoms which is optionally substituted by halogen,
an alkenyl radical with 3 to 4 carbon atoms which is optionally substituted by halogen, Around Rj each hydrogen or one methyl and that other hydrogen and X represent oxygen or sulfur. 2. Octahydropyrindenes according to claim 1, wherein X means oxygen. 3. Octahydropyrindenes according to claim 2, wherein R is an alkyl radical with 1 to 4 carbon atoms, the 2-chloroethyl, Represents 3-chloropropyl or the allyl radical. 4. The compound 1- (ethylthio-carbonyl) -octahydro-1-pyrinden according to claim 3. 5. The compound 1- (n-propylthio-carbonyl) -octahydro-1-pyrindene according to claim 3. 209834/1219 Agripat S.A. 6. The compound 1- (n-butylthio-carbonyl) -octahydro 1-pyrinden according to claim 3. 7. The compound 1- (isopropylthio-carbonyl) -octahydro-1-pyrindene according to claim 3. 8. The compound 1- (sec.Butylthio-carbonyl) -octahydro-1-pyrindene according to claim 3. 9. The compound 1- (3-chloropropylthio-carbonyl) -octahydro-1-pyrinden according to claim 10. The compound 1- (ethylthio-carbonyl) -3-methyloctahydro-1-pyrindene according to claim 11. The compound 1- (n-propylthio-carbonyl) -3-methyloctahydro-1-pyrindene according to claim 12. Process for the preparation of substituted octahydro-1-pyrindenes of the formula I of claim 1, characterized in that an octahydropyrindene of the formula II (II) a) either with a thiocarbon murine halide of the formula III Shark - C - SR (III) Il in the Shark chlorine or bromine and 209834/1219 Agripat S.A. X means oxygen or sulfur or b) with the formation components of a carbonic acid halide of the formula III, namely phosgene or thiophosgene and the alkali metal salt of a mercaptan of the formula IV R-SH (IV) where in the formulas II, III and IV the symbols R, R ,, R ₂ and X have the meanings given under formula I of claim 1, or c) in the presence of an acid-binding agent for the preparation of compounds with X = sulfur with carbon disulfide and an alkylation or. Alkenylating agents of Formula V R-Y (V) or for the preparation of compounds where X = oxygen with carbon oxysulfide and an alkylating or alkylating agent of the formula V in which Ί- halogen denotes an alkoxysulfonyloxy or arylsulfonyloxy radical and R has the meanings given under formula I of claim 1,
implements. 13. Plant-influencing agent, characterized in that it is a compound of the formula as active ingredient 209834/121 Agripat S.A. (i) R is an alkyl radical with 1 to 4 carbon atoms which is optionally substituted by halogen, an alkenyl radical with 3 to 4 carbon atoms which is optionally substituted by halogen, R _n and
ι R _? each hydrogen or one methyl and that other hydrogen and
X oxygen or sulfur mean, together with carriers and / or distribution agents and optionally other herbicidal and pesticidal agents Contains active ingredients. 14. Means according to claim 13, wherein the substituent X in the formula for the specified active ingredients means oxygen. 15. Means according to claim 14, wherein the substituent R in the formula of the specified active ingredients is a Alkyl radical with 1 to 4 carbon atoms, the 2-chloroethyl radical, represents the 3-chloropropyl radical or the allyl radical. 16. Means according to patent claim 15 containing as Active ingredient 1- (ethylthio-carbonyl) -octahydro-1-pyrinden. 17. Agent according to claim 15, containing 1- (n-propylthio-carbonyl) -octahydro-1-pyrindene as Wi rkstoff. 2 Π 9 0 J /> / 1 2 1 9 Agripat S.A. 18. Means according to claim 15> containing 1- (n-butylthio-carbonyl) -octahydro-1-pyrindene as active ingredient, 19. Means according to claim 15 containing l- (isopropylthio-carbonyl) -octahydro-1-pyrindene as active ingredient. 20. Means according to claim 15 containing 1- (see.Butylthio-carbonyl) -octahydro-1-pyrinden as active ingredient. 21. Means according to claim 15, containing as Active ingredient 1- (3-chloropropylthio-carbonyl) -octahydro-1-pyrinden. 22. Means according to claim 15 containing 1- (ethylthio-carbonyl) -3-methyl-octahydro-pyrindene as active ingredient. 23. Means according to claim 15 containing 1- (n-propylthio-carbony 1) -3-methyl-octahydro-pyrindene as active ingredient. 24. Methods for combating weeds and grass weeds in cereals, maize, soybeans, cotton, sugar beets and rice crops, characterized by the use of herbicidally substituted octahydro-1-pyrindenes Formula I of claim 1 or of agents according to claim 13. 25. A method for inhibiting the growth of grasses and cereals, characterized by the use of substituted octahydro-1-pyrindenes of the formula I of claim 1 or of agents according to claim 13. 209834/1219