DE2217697C3 - Means for regulating plant growth - Google Patents

Description

CH ₃

in the X ° the anion of a non-phytotoxic acid and A an optionally by chlorine substituted chain with the structures

(CH ₂ J ₅

- (CH ₂ J ₃ - CHCl-CH ₂ --- (CH ₂ ), - CH = CH-CH ₂ - - (CH ₂ J ₂ -S- (CH ₂ J ₂ - - (CH ₂ J ₂ -SO- (CH ₂ J ₂ - - (CH ₂ J ₂ -SO ₂ - (CH ₂ J ₂ - - (CH ₂ J _n -S-CH ₂ - with η = 2 or 3 or
-CH ₂ -S-CH ₂ -S-CH ₂ -

means.

2. Use of a salt according to claim 1 for regulating plant growth.

The present invention relates to means of regulation of plant growth, which contain cyclic sulfonium compounds as active ingredients, and the Use of these compounds to regulate plant growth.

It is known to use nitrogen-containing compounds such as 1,1-dimethyl-1 - (/ J-chloräthylJ-hydraziniumchloiid (im following CMH abbreviated) (K. H. Koni g, Naturwiss. 55, 217 [1968], and R. W e g 1 e r. Chemistry of pesticides and pesticides, Vol. 2, p. 324, Springer Verlag, Berlin 1970), N, N, N-trimethyl-N-2-chloroethylammonium chloride (hereinafter abbreviated to CCC) (DT-AS 12 94 734) and trialkylsulfonium salts (DT-AS Il 79 044, FR-PA 20 01 298 and FR-PS 15 24 922) to influence plant growth to use. These connections intervene in the physiological processes of the plant Growth and can therefore be used as plant growth regulators.

Typical effects of plant growth regulators include reduction or enhancement of growth in length. Similarly, germ or flower induction can take place, i. H. an influence on the plant's annual rhythm. The formation of side shoots can also result Growth regulators are promoted or inhibited.

Of economic interest, for example, is the prevention of the "storage" of grain in front of the Harvest through growth regulators or the reduction of grass cover on roadsides and on lawns so that frequent mowing can be reduced.

When using the known growth regulators, e.g. B. on cereals in which a ge-CH ₃

in the Χ ^θ the anion of an inorganic or organic, but not phytotoxic acid, preferably bromide or chloride, and A is a chain with the structures optionally substituted by chlorine

- (CH ₂ J ₅ -

- (CH ₂ J ₃ -CHCl-CH ₂ -
- (CH ₂ J ₂ -CH = CH-CH ₂ -
- (CH ₂ J ₂ -S- (CH ₂ J ₂ -
- (CH ₂ J ₂ -SO- (CH ₂ J ₂ -
- (CH ₂ J ₂ -SO ₂ - (CH ₂ J ₂ -
- (CH ₂ J _n -S-CH ₂ - with π = 2 or 3
or

-CH ₂ -S-CH ₂ -S-CH ₂ -

^{z z 2}

means better effects as growth regulators than the known compounds in numerous plants show what can be seen in a reduction in length growth in some plants expresses.

The compounds can also be applied to the plants in conjunction with other crop protection agents, ie together with herbicides, insecticides, but in particular also fungicides. The combined use of the compounds according to the invention with fertilizers, in particular mixing with urea, also proves to be advantageous in practice.
The effect is particularly evident in cereals,

z. B. wheat, rye, barley, rice and oats, but also with dicots (e.g. potatoes, tomatoes, vines, Cotton) and various ornamental plants such as poinsettias and hibiscus. The treated plants accordingly have a stocky habit; a darker blue color can also be observed.

The effectiveness of the compounds is due to the cation, so that the choice of the anion is arbitrary is. However, anions of phytotoxic acids should not be used when solely on influencing of plant growth and not on killing the plants. Suitable Acids are for example: hydrochloric acid, hydrobromic acid, sulfuric acid, carbonic acid, nitric acid, Phosphoric acid, acetic acid, propionic acid, benzoic acid, sulfuric acid monomethyl or ethyl ester, 2-ethylhexanoic acid, acrylic acid, maleic, succinic, adipic acid, formic acid, chloroacetic acid, p-toluenesulfonic acid, Benzenesulfonic acid. The compounds can be supplied to the plants both via the soil, i. H. through the roots as well as by spraying through the leaf. Except for soil and leaf treatment seed dressing can also be carried out. As a result of the relatively high For plant compatibility, the application rate can vary significantly, for example up to 15 kg active ingredient / ha. In general, however, doses of 0.5 to 8 kg / ha are to be regarded as sufficient.

The compounds to be used in the present invention include, for example, those shown below Table listed sulfonium salts.

cation

Anion melting point literature ("C)

- CH ₃

S S-CH ₃

Br 225 *)

Br 193

175

la, Ib, Ic

Bro 240 **) -

Cl "225 1 a

172 2

OS S-CH,

SQJ- 127 **) 2

J "187 5

Br '181-184 4

O ₂ S S-CH ₃ Br 180 *)

^ S-CH ₃ <Qs-CH, J ¹ 125 Br 120-122 S S-CH ₃ J ¹
Br ¹ 85-86 *) <^ S-CH ₃ J ' Cl Cl (strong
hygro
scopic)

be turned. The forms of application depend entirely on the intended use; they should be in ensure a fine distribution of the active substance in each case.

The solution in water can be used to produce directly sprayable solutions. It can but also hydrocarbons with boiling points higher than 150 ° C, z. B. tetrahydronaphthalene or alkylated Naphthalenes, or organic liquids with boiling point

score higher than 150 "C and one or more functional groups, e.g. B. the keto group, the ether group, the ester group or the amide group, this group being a substituent on a hydrocarbon chain or part of a heterocyclic chain Ringes can be used as spray liquids.

Aqueous use forms can be made from emulsion concentrates, pastes or wettable powders (Wettable powders) by adding water

will. To produce emulsions, the substances can be used as such or in a solvent dissolved, by means of wetting or dispersing agents, e.g. B. polyethylene oxide addition products in water or organic solvents are homogenized.

However, it is also possible to prepare concentrates consisting of active substance, emulsifying or dispersing agent and possibly solvent, which are suitable for dilution with water.
Dusts can be obtained by mixing or co-grinding the active substances with a solid carrier, e.g. B. kieselguhr, talc, clay or fertilizers can be produced. The production of granulated agents, for example mixed with fertilizers, is also possible.

The following example describes the preparation of l-methyl-1,4-dithianium bromide. To This method can also be used to synthesize other methyl-substituted sulfonium salts.

45

55

·) Decomposition point. **) Sublimation point.

la = W. M a η sfc I d. Chem. Bit. 19, 2658 266 "(1 HXb).

I b = C. D. N c η i I /. c scu and N. S ca r I a I escu (hem Ber

67B. 1142-1144 (19341. Ic = A.E. Arbuzov and U.M. Zn roast ruva. .l / .vesi

Akad. Nauk S. S. S. R. Otdel Khim. Nauk, 1952. 453 45X to

(Chem. Abstr. 47, 4833 [1953]).

2 = O. M a s s o n, J. Chem. Soc. 49,233,249 (1 XKft |.

3 = F .. V. Bell and G. M. Ben η eil. .1. Chem. Soc 19 "> X

86 92.

4 = IX S t rii mh ο I in. Chem Her. 31 X23 X4I (1900)

(1939). _ft5

s = S. W. L c e and C !. Γ) ο u μ h e r I y. J. Ory. Chem 4. 4X 53

The agents according to the invention can be applied as solutions, emulsions, suspensions or dusts

example 1

3 parts (parts by weight) of 1,4-dithiane are dissolved in 80 parts of acetonitrile and 7 parts of a 5N methyl bromide solution in acetonitrile are added. After 3 days, the precipitate formed is filtered off with suction and dried. To give 2 parts of pure 1-Mcthyl-1,4-dithianium bromide that sublimes in the open tube melting point at 240 ⁰ C with no residue. Another 2 parts of product can be obtained from the mother liquor by concentration.

The biological effects of the new agents are described in the following examples.

Example 2
Effect on rye

Rye grains of the »Petkuser« variety were placed in so-called Neubau pans (diameter 12 cm) in sown loamy sandy soil. The active ingredients were applied immediately after sowing 0.5 mg / vial, 3 mg / vial, 6 mg / vial and 12 mg / vial in aqueous solution on the soil surface injected. The application rates correspond to an application of the active ingredients of 0.5 kg / ha, 3 kg / ha. 6 kg / ha and 12 kg / ha. In addition to the untreated control vessel, various known ones were used as a comparison Active ingredients used. The experiment was carried out under greenhouse conditions. the

The height of growth determined after 20 days is shown in the table below.

In the case of foliar treatment, 13 days after the Application, the following differences in height:

Active ingredient

Height of growth (rel.) With active ingredient concentration from

0.5 mg '3 mg / 6 mg' 12mg ¹ vessel vessel vessel vessel

Control (untreated)
CMH (known)

100 100 100 100 91 88 88 85

(CH ₃ J ₃ S ⁺ Br "(known) - 100-100

CH ₃ CH ₃

S ⁺ -CH Br "- 91-86

CH ₃ CH ₃

(known)

l-methyl-1,4-dithianium chloride

S ⁺ -CH, Br "

88 85 84 76

- 87 - 82

Example 3 Effect on Wheat

As in Example 2, spring wheat of the »Opal« variety was sown and immediately after sowing in Application rates of 3 mg / vessel, 6 mg / vessel and 12 mg / vessel (corresponding to 3, 6 and 12 kg / ha) on the Sprayed floor surface. A foliar treatment was done on 10 cm high wheat plants, 8 days after the sowing. The application rates here were 3 mg / vessel and 6 mg / vessel (corresponding to 3 and 6 kg / ha).

The height of growth determined after 21 days of soil treatment is shown in the table below:

Active ingredient

Height of growth (rel.) With active ingredient concentration of

3 mg / vial

6 mg / vial

12 mg / vial

Control (untreated) 100

CMH (known) -

(CH ₃ ) ₃ S ⁺ Br "(known) 100

CH ₃ CH ₃

100

74

S ⁺ -CH Br-

\
CH ₃

CH ₃
(known)

l-methyl-1,4-dithianium chloride

1 -Methyl-S ^ dehydro-1 -thiacyclohexanium bromide

S'-CH, Br

78 -

- 65

72

73

100

66

100

69

56

65

Active ingredient Height (rel.) At
concentration of 3 mg /
GeSB Effective loft 1.5 mg /
vessel 100 6 mg /
vessel Control (untreated) 100 90 100 CMH 93 86 86 1 -Methyl-1,4-dithianium-
chloride 90 87 83 1 -Methyl-S ^ -dehydro-
i-thiacyclohexanium-
bromide 90 85 By S ρ i e 1 4

Effect on barley

Another test with spring barley was carried out under the same test conditions as in Example 2 of the »Breuns Wisa« variety. The application rates were above the ground for the treatment 5.5 mg / vessel, 6 mg / vessel and 12 mg / vessel (corresponding to 1.5, 6 and 12 kg / ha) for foliar treatment 1.5 and 3 mg / vessel (corresponding to 1.5 and 3 kg / ha).

23 days after the treatment over the ground, the following differences in length growth were observed can be determined:

45

Active ingredient Height (rel.) At 6 mg / Active ingredient concentration of GcS ß 1.5 mg / 100 12 mg / vessel 76 vessel Control (untreated) ' 100 75 100 CMH 89 75 1 -Methyl-1,4-dithianium- 81 71 chloride

The foliar treatment was carried out at a plant height of 10 cm; after a further 12 days the following differences in growth:

Active ingredient

Height (rel.) With active ingredient concentration of

1.5 mg / vial 3 mg / vial

65

Control (untreated) 100 100

CMH 98 98

1-methyl-1,4-dithianium-97 95
chloride

l-methyl-3,4-dehydro- 97 91
1 -thiacyclohexanium bromide

Example 5

90 parts by weight of the compound according to Example 1 are mixed with 10 parts by weight of N-methyla-pyrrolidone and receives a dispersion that is suitable for use in the form of tiny drops.

Example 6

20 parts by weight of the compound according to Example 1 are dissolved in a mixture consisting of 80 parts by weight of xylene and 10 parts by weight of the adduct from 8 to 10 moles of ethylene oxide to 1 mole of Ό1-acid-N-monoethanolamide, 5 parts by weight of the calcium salt of dodecylbenzenesulfonic acid and 5 parts by weight of the adduct of 40 mol of ethylene oxide consists of 1 mole of castor oil. Pouring the solution into 100,000 parts by weight of water and finely distributing it therein gives an aqueous dispersion which Contains 0.02 percent by weight of the active ingredient.

Example 7

20 parts by weight of the compound according to Example 1 are dissolved in a mixture consisting of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 7 moles of ethylene oxide and 1 mole of isooctylphenol and 10 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. Through Pouring the solution into 100,000 parts by weight of water and finely distributing it therein gives an aqueous solution Dispersion containing 0.02 percent by weight of the active ingredient

Example 8

20 parts by weight of the compound according to Example 1 are dissolved in a mixture consisting of 25 parts by weight of cyclohexanol, 65 parts by weight of a mineral oil fraction with a boiling point of 210 to 280 ³ C and 10 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. Pouring the solution into 100,000 parts by weight of water and finely distributing it therein gives an aqueous dispersion which contains 0.02 percent by weight of the active ingredient.

Example 12

Spring wheat of the »Opal« variety was sown in new building trays on a light sandy soil, and immediately after sowing these were with the active ingredients in application rates of 3 mg / vessel and 12 mg / vessel (corresponding to 3 and 12 kg / ha) sprayed. The height of the wheat plants determined after 18 days is shown in the table below:

> 5

Active ingredient Height of stature (rcl.) At effective substance concentrations of 3 mg / Gcfali 12 mg / Serenity Control (untreated) 100 100 CCC 71 66

C S ⁺ -CH ₃ Br

64

60

Example 13

In the same way as in Example 12, summer rye of the cultivar "Petkuser" was sown and treated. The height of the rye plants, also determined after 18 days, is shown in the following table:

3 ° Active ingredient

40

Example 9

20 parts by weight of the active ingredient according to Example 1 are mixed with 3 parts by weight of the sodium salt Diisobutylnaphthalene-α-sulfonic acid, 17 parts by weight of the sodium salt of a lignosulphonic acid from a sulphite waste liquor and 60 parts by weight of powdered Silica gel mixed well and ground in a hammer mill. By distributing the Mixing in 20,000 parts by weight of water gives a spray liquor containing 0.1 percent by weight of the active ingredient contains

Example 10

3 parts by weight of the compound according to Example 1 are combined with 97 parts by weight of finely divided kaolin Intimately mixed, a dust containing 3 percent by weight of the active ingredient is obtained in this way contains.

Example 11

30 parts by weight of the compound according to Example 1 are mixed with a mixture of 92 parts by weight powdered silica gel and 8 parts by weight of paraffin oil on the surface of this silica gel was sprayed, intimately mixed. This gives a preparation of the active ingredient with good quality Adhesiveness

Control (untreated)
CCC

Height of growth (rel.) At effective • ß 12 mg / substance concentrations of 100 vessel 2 May 94 100 91

⁺ -CH,

84

Example 14

Wheat plants of the variety »Opal« were planted in a vegetation experiment on a loamy sandy soil at a height of about 30 cm with the equivalent of 0.75 kg of active ingredient / ha of the various active ingredients. After the wheat had ripened, the length and diameter of the stalk were measured. It resulted the following values:

55 Active ingredient Straw length (cm) HaIm-
diameter relative absolutely relative 100 absolutely (mm) (cm) 86 (mm) 100 60 Untreated 84 3.7 102 CH ₃ CH ₃
S ⁺ -CH Br "
/ \
CH ₃ CH ₃ 72 3.8 (known)

809 607/229

continuation

Active ingredient

?> ⁺ —CH ₃ Br "
S ⁺ -CH ₃ Br "

Halmlangc

absolute relative (cm) (cm)

Haim diameter

absolute relative (mm) (mm)

85 -

79 3.9

105

ίο

Immediately afterwards, the active ingredient was applied to the soil as a solution in amounts equivalent to 3 kg / ha injected. The height of growth determined after 18 days is shown in the table below.

Active ingredient

Height of growth (rel.) With effective concentrations of 3 mg / vessel

Untreated 100

1-methyl-1,3-dithianium-83
iodide

Example 15 Effect on cotton

Cotton plants were grown in new building pans up to a height of about 12 cm (1st pair of leaves) and with aqueous solutions of the active ingredient in amounts corresponding to the application of 1.5 and 6 kg / ha sprayed. After a test duration of 48 days, the heights of the plants were determined.

"Active ingredient

Height (rel.) With active ingredient amount of

1.5 mg / vial 6 mg / vial

Untreated 100 100

1 -Methyl-1,3-dithianium- 85 75

bromide

S ⁺ -CH, Br "

Example 16 Effect on Barley

Barley grains of the »Breuns Wisa« variety were sown in new building trays in loamy sandy soil. S ⁺ -CH,

ze B e i s ρ i e 1 17

Effect on wheat

Wheat grains of the »Opal« variety were sown in new building trays in loamy sandy soil and the soil is sprayed with the active ingredient (corresponding to 3 and 12 kg / ha), as described in Example 16. the The following table shows the heights of growth determined after 18 days.

Active ingredient

Height of growth (rel.) With active ingredient concentrations of

3 mg / vial

12 mg / vessel

Untreated

l-methyl-3-chlorothianium chloride

100
89

100
85

—CH ₃ er

Claims (1)

Patent claims: 1. Agent for regulating plant growth containing a salt of the general formula penetrated growth to prevent storage is to be achieved, the effect is bad. It has been found that compounds of the general formula