DE1221841B - Selective herbicides - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY GERMAN ^ fl9W ^ PATENT OFFICE

EDITORIAL

Int. Cl .:

AOIn

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German class: 451-19 / 02

1221841
B 80219IV a / 451
January 22, 1965
June 28, 1966

It is known from Weed Res., 1960, Vol. 2, pp. 130 to 135 that an 1- (2-bicyclo- [3,3,0] -octyl) -3,3-dimethylurea from a melting point of 150 to 151 ° C, which, according to our investigations, is in the essentially the endo compound, a certain, if only minor, general herbicidal Has an effect. However, this effect is by no means sufficient for practical use. aside from that is l-cyclooctyl-S ^ -dimethylurea (OMU, German patent specification 1 027 930) known as an active ingredient of a selective herbicide. The connection owns however, on various dicotyledon weeds, e.g. B. dead nettle and sorrel, an unsatisfactory one Effect.

It has now been found that ureas of the formula Selective Herbicides

R - NH - C - NC

^ CH ₃

in which the remainder Ri denotes the methyl, methoxyl or l-methyl-2-propynyl radical means and the grouping R - NH is derived from the amines

a) exo-bicyclo- [3,3,0] -octyl-amine-2,

b) endo- and exo-bicyclo-ß ^ OJ-octyl-amine-S,

c) exo-bicyclo- [3,2,1] -octyl-amine-8,

have a better herbicidal activity than the abovementioned compounds. The new ureas are selective on the crops maize, potatoes, cereals, cotton, rice and beans.

The amines required to produce the new ureas can be produced as follows:

Bicyclo- [3,3,0] -octen-2 (German Auslegeschrift 1 167 824) is subjected to the so-called Ritter reaction (cf. Houben-Weyl, Vol. XI / 1, p. 994, Georg Thieme-Verlag, Stuttgart, 1957) and hydrolyzes the acylamines formed to the corresponding amines. The resulting amine mixture can be separated into four fractions by preparative gas chromatography, of which the first fraction exo-bicyclo- [3,3,0] -octyl-amine-2, the second endo- and exo-bicyclo-P ^ OJ-octyl-amine-S, the third contains endo-bicyclo- [3,3,0] -octyl-amine-2 and the fourth contains exo-bicyclo- [3,2,1] -octyl-amine-8.

Known methods analogously can be used both from the individual fractions and from the amine mixture the ureas dissolved in by reaction with the corresponding carbamic acid derivatives a hydrocarbon and in the presence of an acid binder or a catalyst Applicant:

Aniline & Soda Factory in Baden

Aktiengesellschaft, Ludwigshafen / Rhein

Named as inventor:

Dr. Adolf Fischer, Mutterstadt (Palatinate);

Dr. Hans Kiefer,

Dr. Ludwig Schuster, Ludwigshafen / Rhine;

Dr. Gustav Steinbrunn, Schwegenheim (Palatinate) - -

will. The ureas can also be obtained by converting the amines or the amine mixture from the Ritter reaction into the isocyanates or carbamic acid chlorides and subsequent conversion with the corresponding secondary amines.

For example, when the four fractions are reacted with dimethylcarbamic acid chloride, fraction 1 forms 1- (exo-2-bicyclo- [3,3,0] -octyl) -3,3-dimethylurea (I) with a melting point of 138 ° to 139 ° C, from fraction 2 of the l- (exo and endo - 3 - bicyclo - [3,3,0] - octyl) - 3,3 - dimethylurea (II) with a melting point of 154 to 155 ° C, from fraction 3 the L- (endo-2-bicyclo [3,3,0] octyl) -3,3-dimethylurea (III) of melting point 156-157 ⁰ C, and from the fraction 4 of l- (exo-8-bicyclo - [3,2,1] -octyl) -3,3-dimethylurea (IV) from melting point 152 to 155 ° C.

the mixture of amines is transferred from the Ritter reaction without isolating the individual components directly into the corresponding ureas, a mixture (V) is obtained which for Ri = CH3 has a melting point of 132 to 134 ° C and the following composition determined by infrared spectroscopy having:

I ~ 30%

II ~ 30%

III 5 to 10%

IV ~ 30%

Because of the small proportion of the less effective component III and the practically the same good effectiveness of components I, II and IV, it is recommended that the easily accessible mixture to use the urea V as an active ingredient.

609 607/378

The mixture of ureas V with Ri = OCH3 melts at 46 to 48 ⁰ C. When the mixture of ureas with V

H
Ri = CC ^ = C ■

CH ₃

-H

it is a syrupy mass. "

The agents can be in the form of solutions, emulsions, suspensions or dusts, for example can be applied. The forms of application depend entirely on the intended use; they should ensure a good distribution of the active substances in each case. Watery Dispersions can be prepared with the aid of conventional dispersants.

Medium-sized mineral oil fractions are used to produce solutions that can be sprayed directly to a high boiling point, such as kerosene or diesel oil, also coal tar oils and vegetable oils of animal origin, as well as cyclic hydrocarbons such as tetrahydronaphthalene and alkylated Naphthalenes, using suitable auxiliary solvents, e.g. B. xylene into consideration. solutions in low-boiling solvents, such as. B. alcohols, ketones, ethers or low-boiling hydrocarbons, are less suitable for direct application than for combination with suitable emulsifiers for the production of concentrates for the preparation of aqueous Emulsions.

Dusts can be mixed or ground together with the active substances a solid carrier. Examples of these are: calcium carbonate, talc, Diatomaceous earth, calcium phosphate, boric acid, also flour, cork flour, coal and other materials. On the other hand, the substance can also be applied to the carrier substances by means of a volatile solvent be applied. In this way it is possible to obtain granules that can be sprinkled.

The biological spectrum of activity can be broadened by adding substances with bactericidal, fungicidal and especially with herbicidal properties, as well as through combination with fertilizers.

Example 1.

Ze'a mays (maize), Hordeum vulgäre (barley), Triticum vulgäre (wheat), Avena sativa (oats), Seeale cereale (rye), Gossypium sp. (Cotton), Oryza sativa (rice), Phaseolus vulgaris (beans), Poa annua (! Annual bluegrass), Sinapis arvensis (field mustard), Vicia sp. (Vetch), Rumex sp. (Sorrel). And Lamium aniplexicaule (dead nettle surrounding the stalk) in plastic pots filled with loamy sandy soil and sown on the same day with hexo ^ -Bicyclo-P ^ Oj-octylH ^ -dimethylurea, m.p. 138 to 139 ° C (I), l- (exo - and endo-3-bicyclo [3,3,0] octyl) -3,3-dimethylurea, mp 154-155 ⁰ C (II), L- (endo-2-bicyclo [3.3. 0] octyl) -3,3-dimethylurea, mp. 156-157 ⁰ C (III), l- (exo-8-bicyclo [3,2, l] -octyl) -3,3-dimethylurea, m.p. 152 to 155 ° C (IV), mixture of I, II, ΙΠ and IV, melting point 132 to 134 ° C (V), and in comparison therewith treated l-cyclooctyl-S ^ -dimethylurea (VI). The application rates were in each case 1 kg of active ingredient per hectare in an amount of water corresponding to 500 liters per hectare. After a test duration of 4 weeks, the following result was found:

0 I. 10 II 0
0 III Really material IV V 10 VI 20th Corn 0
0 0
0
until 10
10 0
0
0- 0 0
0
0 0
0
10 0 to 10
0
0 to 10 10 until
10
10 potatoes 0 until
until 10 . . 0
0 0 0
0 10
10 0 to 10
0 to 10 20th until
90 20th barley until
0 0
0 0
0 10
0 0 to 10
0 0 until
10 30th Wheat . . ... 0
80 0 10
90 0 0 0 0 to 10 70 until 10 oats 40 until
until
80 50 0 to 10
90
90 0
until
until 10
10 0 until 10
80
80 0
90
90 to 100 30th 10
90
until Horses ... until 50 until 10 40 until 50 60 to 70 20th until 80 cotton 70
70 70 to 80
70 to 80 until
O 10 70
70 70 to 80
90 until
30th 40 rice 30th Beans annual bluegrass ....
mustard Vetch sorrel Dead nettle

0 = without damage. 100 = total damage.

The same biological effectiveness as V have the corresponding urea mixtures in which Ri

a) has the meaning methoxyl (melting point of the mixture 46 to 48 ⁰ C) and

b) has the meaning of l-methyl-2-propynyl (syrup).

Example 2

The plants Zea mays (maize), Hordeum vulgare (barley), Triticum vulgare (wheat), Gossypium sp. (Cotton), Oryza sativa (rice), Secale cereale (rye), Avena sativa (oats), Phaseolus vulgaris (Beans), Poa annua (annual bluegrass), Sinapis

arvensis (field mustard), Vicia sp. (Vetch), Rumex sp. (Sorrel) and Lamium amplexicaule (dead nettle surrounding the stalk) were at a height of 4 to 14 cm with 1- (exo-2-bicyclo- [3,3,0] -octyl) -3,3-dimethylurea, mp 438 to 139 ⁰ C (I), l- (exo- and endo-S-bicyclo-is ^ .djioctyli-S ^ -dimethylurea, melting point 154 to 55 ° C (II), l- (endo-2-bicyclo- [3, 3.0] octyl) -3,3-dimethylurea, m.p. 156 to 157 ° C (III),

Hexo-S-Bicvclo-p ^ ll-octyl ^^ - dimethymarnea, m.p. 152 to 155 ⁰ C (IV), mixture of I, II, III and IV, m.p. 132 to 134 ° C (V), and im For comparison, I-Cy ^ looctyl-3,3-dimethylurea (VI) treated. The application rates were in each case 1 kg of active ingredient per hectare in an amount of water corresponding to 5001 per hectare. After 3 weeks the following result was found:

I. II Really
III material
IV V VI Corn '. 0 0 0 0 0 0 potatoes 0 0 0 0 5 10 barley 0 0 to 10 0 0 5 20th wheat 0 0 to 10 0 0 10 to 20 20th oats 0 0 to 10 0 0 10 20th rye 0
10 10
10 0
10 0
10 to 20 10
10 10 to 20
10 to 20 cotton 0 0 0 0 0 0 rice 0 0 0 0 0 0 Beans 80
70 to 80 80 to 90
80 . 10
10 90
70 to 80 90
80 to 90 70
70 to 80 annual bluegrass ....
Mustard 50 to 60 60 5 60 60 40 Vetch 70 to 80
70 to 80 70 to 80
70 to 80 5
10 70
70 80
70 to 80 30th
20th sorrel Dead nettle .... ....

^: total damage.

As can be seen from the examples, they have the same biological effectiveness as V. Compounds I. II, IV and the mixture V in the 35 the corresponding urea mixtures in which

equal to III and VI a better herbicidal effect R _x

of vetch. Sorrel and dead nettle if a) has the meaning methoxyl (melting point

good plant tolerance on maize, potatoes, the mixture 46 to 48 C) and

Grain, cotton. Rice and beans. b) has the meaning of l-methyl-2-propynyl (syrup).

Claims (1)

Claim: Selective herbicide, characterized by the content of a urea derivative the formula R - NH - C - N < / CH ₃ 2-propynyl radical and the grouping R - NH is derived from the amines a) exo-bicyclo- [3,3,0] -octyl-amine-2 or b) endo- and exo-bicyclo-β ^ OJ-octyl-amine-S or in the Ri den methyl, methoxyl or 1-methyl- 50 c) exo-bicyclo- [3.2, l] -octyl-amine-8. 609 607/378 7.66 © Bundesdruckerei Berlin