DE2601447A1 - CYCLOHEXE ESTER - Google Patents

Description

The invention relates to new cyclohexene ester processes for their preparation and their use as selective herbicidal agents.

The compounds according to the invention have the general formula

-R

in the R. a lower alkyl group with up to six carbon atoms, Rp is a lower alkyl group with up to six carbon atoms or a lower alkenyl group with up to six carbon atoms, R-, a hydrogen atom or a lower alkoxy carbonyl group with up to six carbon atoms, R is an aliphatic or aromatic ester

609831/0963

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residue of a di- or tribasic acid and ^ .n 2 or 3 means. 2601 4 A

Preferred compounds are preferred because of their efficacy as herbicides in low levels and their stability those of the formula

^R 1 _V / ^N - ° ^R 2

R ₁ .N-OR- ¹ V ²

[II]

CH ₃

in the R .. an ethyl or propyl group, Rp an ethyl or Allyl group and R ^ is a hydrogen atom or a Means methoxycarbonyl group.

Particularly preferred because of their herbicidal effectiveness

Bis / 2- (N-allyloxybutyrimidoyl) -5,5-dimethyl-3-oxo-1-cyclohexen-1-yl7-terephthalate,

Bis ^ 2 "- (H-allyloxybutyr imidoyl) -5,5-dimethyl-3-oxo-1 -cyclohexen-1-yl7-isophthalate,

Bis ^ 2- (IT-allyloxybutyrimidoyl) -5,5-dimethyl-3-oxo-1-cyclohexene-1 -yl7-1> 3-benzene disulfonate,

To _i / 2 "- (2i-allyloxybutyrimidoyl) -4-niethoxycarbonyl-5,5-diraethyl-3-0X0-1 cyclohexen-i-yl ^ -telephthalat.

The compounds of the invention can be prepared according to the following equation:

CH ₃ CH ₃

[III]

+ R (CA) _n

[IV]

L Ch ₃ CH ₃ ;

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260H47

in the

, R, and η have the meaning given

■ The starting substance III can be according to the following
Equations are made:

CH ₃ CH ₃

[V]

[VI]

R ₁

CH

M HONH ₂ -HCA -

or HONHSO ₃ Na

:

[VII]

[VIII]

NH-O-R

NH OR

^R.

CHj CHj

[III]

CHj CHj

[III]

where M is a hydrogen or alkali atom (preferably Sodium) and X is a halogen atom. The compound of lOrmel III can be in the following two tautomeric forms are present.

CH ₃ CH ₃

[III]

CH ₃ CH ₃

[IX]

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2601U7

In the practical implementation, the Alkali salt of the starting compound III prepared by treating the compound with sodium or potassium hydroxide in an organic solvent.

This alkali salt is reacted with the compound of the general formula IV in an inert solvent after it has been separated from the reaction mixture or as it is incurred. The compound III can.also with compound IV in the presence of alkali salts such as sodium or potassium hydroxide are implemented.

Acetone, ether, alcohol, benzene, toluene, chloroform, ethyl acetate, etc. can be used as the inert solvent will.

Typically, temperatures in the range of minus 20 ⁰ C are applied to the Siedepumkt of the solvent, and preferably below room temperature for the above reaction employed and the reaction is completed within about 15 minutes to 5 hours.

After completion of the reaction, the solvent used becomes if necessary replaced by another solvent and then the reagent mixture with an alkaline one Solution and water washed and dried. The solvent is then evaporated off under reduced pressure and obtaining the raw product in the form of crystals or as a liquid.

The crude product can be purified by recrystallization or column chromatography.

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The structure of the purified compound obtained can be confirmed by the elemental analysis of the NMR spectrum or the IR spectrum, etc. identified "or" confirmed will.

Acid chlorides of the formula IV which can be used as starting substances are, for example, the chlorides the following or 3-basic acids are suitable.

a) Aliphatic acids

Malonic acid, succinic acid, glutaric acid, adipic acid, azaleic acid, sebacic acid, methylmalonic acid, methyl- .. -succinic acid, maleic acid, phthalic acid, cyclohexane-1,4-dicarboxylic acid etc.

b) phthalic acid derivatives

Terephthalic acid, isophthalic acid, phthalic acid, 1,3,5-benzenetricarboxylic acid and the corresponding alkyl- or halogen-substituted compounds, tetrahydrophthalic acids bicyclo / 2,2,1_7 * ieptane-2,3-dicarboxylic acid (3,6-methylenetetrahydrophthalic acid), 7- oxabicyclo / 2 , 2 _/ jJ7heptane-2,3-dicarboxylic acid etc.

c) sulfonic acids

1,3-benzenedisulfonic acid, 1,3,5-benzenetrisulfonic acid, 3-carboxyl benzenesulfonic acid

COOH

and the corresponding alkyl or halogen substituted Links.

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The invention is illustrated in more detail by the following examples.

example 1

Preparation of the compound or formula

(Connection 1)

5 g of 2- (1-allyloxyaminopropylidene) -5,5-dimethylcyclohexane-1,3-dione were dissolved in 50 ml of acetone and 2 ml of an aqueous solution containing 0.9 g of sodium hydroxide, . added and the resulting solution was stirred at room temperature for 1.5 hours the sodium salt of 2- (1-allyloxyaminopropylidene) -5,5-dimethylcyclohexane-1,3-dione.

Kach cooling, the resulting solution was added 1.6 g of terephthalic acid dichloride are added at a temperature of 0 to 5 ⁰ O to the solution and stirred for 30 minutes at 0 to 5 ⁰ C and a further two hours at room temperature.

At the end of the reaction, the precipitated sodium chloride was removed, the acetone was distilled off , the residue was poured into 100 ml of water and extracted with chloroform.

The obtained chloroform layer was washed with an aqueous solution containing sodium hydroxide and washed with water. The chloroform layer was

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dried over sodium sulfate and the chloroform was distilled off. When the residue obtained was recrystallized from acetone, 4.3 g of the desired product Ip 122 to 125 ^° C. were obtained

Example 2

Preparation of the compound of the formula Ii-O-CH CH = _{CH_C 0} H- .NO-CH ₀ CH = CH ₀

0CO-CH ₀ CH - COO. ^^ ν ^, Ο / λ

2 2 \\ (connection 2)

CH ₃ ^ CH ₃

5 g of 2- (1-allyloxyaminopropylidene) -5,5-dimethylcyclohexane-1,3-dione were dissolved in 50 ml of acetone and 2 ml of an aqueous solution containing 0.9 g of sodium hydroxide were added. The resulting solution was stirred for 1 hour at room temperature, the sodium salt of 2- (1-allyloxyaminop23opylidene) -5 »5-dimethylcyclohexane-1,3-dione being formed. After cooling the solution, 1.5 g of succinic acid dichloride was slowly added to der.Lösung and stirred for 30 minutes at 0 to 5 ⁰ O and further 2 hours at room temperature. After the reaction had ended, the precipitated sodium chloride was removed, the acetone was distilled off and the residue

water
poured into 100 ml and extracted with chloroform.

The resulting chloroform layer was washed with an aqueous solution containing 5 % sodium hydroxide and with water. The chloroform layer was dried over sodium sulfate and the chloroform is distilled off _t Beira recrystallization of the obtained residue from η-hexane gave 2.5 g of the desired

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Product. Pp. 71 to 74 ⁰ C

Example 3

Preparation of the compound of the formula C ₂ H _5x ^ nO-CH ₂ CH = CH ₂

oco-r ^ v — coo _v ^ k_o '(compound 3)

5 g of 2- (1-allyloxyaminopropylidene) -5,5-dimethylcyclohexane-1,3-dione were dissolved in 40 ml of acetone and 2 ml of an aqueous solution containing 0.8 g of sodium hydroxide were added. The resulting solution was stirred for 1 hour at room temperature, the sodium salt of 2t (1-allyloxyarainopropylidene) -5 _f 5-dimethylcyclohexane-1,3-dione being formed. On concentration, the acetone and the water of the reaction solution distilled off and a further 40 ml of acetone were added to the remaining material / while cooling in ice water, 1.5 g of adipic acid chloride were added dropwise to the acetone solution and the mixture was stirred at room temperature for 1 hour. After the acetone had been distilled off, the reaction mixture was poured into ice water and extracted twice with a mixture of η-hexane and ether (1: 1). The organic layer was washed with an aqueous solution containing 10% by weight of sodium hydroxide and then washed twice with water and dried over magnesium sulfate. When the organic solvent was distilled off under reduced pressure, 3.7 g of the desired product were obtained. Ι "ρ. 52 to 54 ⁰ C.

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Example 4

Preparation of the compound of formula

(Compound 11)

CH ₃ -CH ₃

The procedure was as in Example 1, "where 3.9 g of 2- (1-allyloxyaminobutylidene) -5 '»5-diraethylcyclo hexane-1,3-dione and 2.5 g m ~ benzenesulfonyl chloride were applied. 3.5 g of the desired product with a refractive index of η ^ 1.5277 were obtained.

Example 5

Preparation of the compound of formula

NO-CH ₀ CH = CH ₀ ^{2 2}

(Connection Η)

4.5 g of 2 - (- i-allyloxyaminopropylidene) -5,5-diraethylcyclohexane-1,3-dione were dissolved in 50 ml of acetone and 2 ml of an aqueous solution containing 0.7 g of sodium hydroxide were added. The solution was stirred for 1 hour at room temperature, the sodium salt of 2- (1-allyloxyaminopropylidene) -5,5-dimethylcyclohexane-1,3-dione being formed.After _{the solution had cooled, 3 g of 2,3} 5,6-} Tetrachloroterephthalic acid dichloride was slowly added at a temperature of 0 to 5 ° C. and the mixture was stirred at this temperature for 30 minutes and at room temperature for a further 2 hours. After the completion of the reaction, the precipitated sodium chloride was removed and the acetone was distilled off. The residue was poured into an aqueous solution containing 4% by weight of sodium hydroxide and the insoluble white crystals were filtered off.

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After washing these crystals with ether, 5.5 g of the desired product were obtained in the form of a white state. Pp. 132-133 ⁰ C (dec.).

Example 6

Preparation of the compound of formula

(Compound 15)

CH

It would work according to Example 1, using 4.5 g of 2- (1-allyloxyaminopropylidene) -5,5-dimethylcyclohexane-1,3-dione and 1.6 g of trimesoyl chloride. The reaction mixture was extracted with ether instead of chloroform. 4 g of the desired product were obtained in the form of an oil with a refractive index of n ² ^ 1.5246.

Example 7 Compound of formula ₂ . (Connection 18) Making the H = CH ₂ C ₃ H _7x ^ NO-CH ₂ CH = CH P M XT Pi PU P '
^C 3 ^H 7 _V / -0- ^CH 2 ^C ΟγΛγΟ-CO- ^ k ^ \ C00CH ₃ CH ₃ OCO / L ^ J CH ₃ CH ₃ ^H CH ₃ ¹ CH ₃

10 g of 2 ^ (1-N-allyloxyaminobutylidene) -4-methoxycarbonyl-5,5-dimethylcyclohexane-1,3-dione were dissolved in 80 ml of acetone, and 8 ml of an aqueous solution containing 1.23 g of sodium hydroxide were added. While cooling the obtained

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Solution were 3 »14 g of terephthalic acid dichloride.in
30 ml of acetone were added dropwise and, after stirring for one hour at room temperature, the precipitate was filtered off and the acetone was distilled off.

The residue was extracted with chloroform containing the chloroform layer with an aqueous solution 5 wt .- $ sodium hydroxide and then washed with water.

After the chloroform layer was dried over sodium sulfate, the chloroform was distilled off. 8.4 g of the desired product were obtained as an oily substance with a refractive index η i. 1.5215.

Examples of compounds which can be used according to the invention are given in Table 1 below
specified.

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Tabel

CT) O CO CO CO

Connecting
dungs Ni *. Structure formula Chemical name Mp 122-125 ° C 1 C ₂ H ^ NO-CH ₂ CH = CH ₂ C ₂ H _5x ^ NO-CH ₂ CH = CH ₂
o> Y ^ y-oco— (Cy coo— ^^ γθ '
CH ₃ CH ₃ 3 3 Bis [2-N-allyloxypropionimidoyl) -
5, S- ^ dimethyl-S-oxo-1-cyclohexene-
ly £ -] -1 he ephthala t Mp. 71-74 ⁰ C
I. 2 C ₀ H, NO-CH = CH ₀ CH CH ^ NO-CH ₉ CH = CH
Oc ^ A ^ O-COCH ^ Hj.COO -—ί ^ ί ^ γ ^
'CH ₃ CH ₃ , ^CH 3 ^CH 3 Bis 12- (N-allyloxypropionimidoyl) -
. SS-diethyl-S-oxo-l-cyclohexeiv-
ly &] - succinate n ³ p * ⁵ l, 5233 3 ρ Tj ν η pil ρτϊ-ptJ P IJ TVT C \ PU PTJ = PTJ
L ₀ Il- ΛΝ — U — IjIX «UtI = VJtI- U ₀ H- IN — U- .UtInVJtI = LItI ₀
Ofejj / ^ r — OCO ( ^/ r ^: \\ —COO ^ -— ^ ii ^ Vj-s: 0
"- 'i'
Bis [2-N-allyloxypropionimidoyl) -
5, S-dimethyl-S-oxo-l-cyclohexenr-
l-yÄ3-isophthalate 29
n J 1.5292 4th C ₂ H _5n ^ NO-CH ₂ CH = CH ₂ C ₂ H ₅ ^ ^ -0-CH ₂ CH = CH ₂
0a / V-0C0-y ^ COO flT ⁰
ptl - ^ 7- <ti CH "'^ CH" Bis [2- (N-allyloxypropionimidoyl) -
5, S-dimethyl-S-oxo-l-cyclohexene
ly £] phthalate

O CO OO co

O CD cn

5 C ₃ H ₇ ^ ^ NO-CH ₂ CH = CH ₂ C ₃ H _7x ^ NO-CH ₂ CH = CH ₂
O ^ y ^ sj-OCO Oj) COCk ^^ vpiO
CH ₃ ^ CH ₃ CH ₃ XcH ₃ Bis [2- (N-allyloxybutyrimidoyl) -
5, S-dimethyl-β-oxo-1-cyclohexene
1-yJl] terephthalate Mp, 98-100 ⁰ C 6th C ₃ H ₇ ^ ^ NO-CH ₂ CH = CH ₂ C ₃ H ₇ NO-CH ₂ CH = CH ₂
• C y
O ^^^ p-OCO-i- ^ j COO- \ ^ f
CH ₃ - ^ CH ₃ ^ a ^^^ ^CH 3 Bts [2- (N-allyloxybutyrimidoyl) -
5, S-dimethyl-S-oxo-1-cyclohexene-
1-yE] isophthalate n ³ ° 1.5243 7 · C ₀ H NO-CH = CH ₀ CH ₀ C _{0 1} h. NO-CH ₀ CH = CH ₀
² \ / ^{2 2 25} N ^ ^{2 2}
CC
O ^ Y ^ pO-CO- (CH ₂ ) ₇₇ CO-O- ^ y = o
CH ₃ ^ CH ₃ CH ₃ - ^ CH ₃ Bis [2- (N-allyloxypropionimidoyl) -
5, S-dimethyl-S-oxo-l-cyclohexene -
l-yÄ] azelate n ² ^ ' ⁵ l _t 5048 8th C, H_ .NO-CH ₀ CH = CH ₀ C ₃ H .. NO-CH ₀ CH = CH ₀
3 7 ^ ;? 2 2 3 7 _χ> ^ 2 2
. o - ^ - ^ pO-co- (CH ₂ ) ₇ -co-o- ^ i = ^:: N === o
σΗ2><0Η_3; CH ₃ ^ CH ₃ Bis [2- (N-allyloxybutyrimidoyl) -
SjS-dimethyl-S-oxo-1-cyclohexene-
ly &] - azelat n "1, ^ 993 9 C, H ₇₁ NO-CH ₀ CH = CH ₀ C "Η-, NO-CH ₀ CH = CH ₀
O = J ¹⁵ VO-Co- (CH ₂ ), -C0-0 ~ fy = 0
CH ₃ → CH ₃ CH ₃ → CH ₃ Bis [2- (N-allyloxybutyrimidoyl) -
5, S-dimethyl-S-oxo-l-cyclohexene
ly £] -adipate n ¹ ^ 1.5038

is

ro

CD

CD

-O-CH ₂ CH = CH ₂

0-C0-

₅ ^ N

CH ₃ bis [2- (N-allyloxypropionimidoy1) -5, S-dimethyl-S-oxo-1-cyclohexenyl-yE] -adipate

Fp. 52-54 ⁰ C

^C 3 \ ^ -0-CH ₂ CH = CH ₂

0-SUN,

-SO ₂ -O

CH ₃ ^ CH ₃

^CH 3 ^CH 3 bis [2- (N-allyloxybutyrimidoyl) -SjS-dimethyl-S-oxo-1-cyclohexenl-yE] -l, 3-benz <oldisulfonate

° 1.5277

C ₂ H ₅

-O-CH ₀ CH = CH ₀ C ₀ H, NO-CH ₀ CH = CH ₉ -2 2 2 -S _n μ 2 2

CH ₃ - ^ CH ₃

CH ₃ ^ CH ₃ bis [2- (N-allyloxypropionimidoyl) -SjS-dimethyl-S-oxo-1-cyclohexene-1-yE] -1, 3-benzol disulfonate

1.5340

C ₀ H, NO-CH = CH ₀ CH ₀ C ₀ H, NO-CH = CH ₀ CH ₀

0 = f ^ pO-CO - (H V-CO-O

CH ₃ ^ CH ₃ bis [2- (N-allyloxypropionimidoyl) -5, S-dimethyl-S-oxo-1-cyclohexenl-yE] -1, 4-cyclohexane_dicarboxylate

C ₀ H, .NO-CH = CH ₀ CH ₀ C _{0 1} h. , NO-CH ₀ CH = CH ₀

CH ₃ -CH ₃

ro-co- <Cy- coca CS,

Bis [2- (N-allyloxypropionimidoyl) - · S.S-dimethyl-S-oxo-1-cyclohexen-1-yJl] -2,3,5,6-tetrachlor., Terephthalate

• 132-133 ° C (dec.)

CH ,. Ii-O-CH ₀ CH = CH ₀ C _O H_ NO-CH-CH = CH-

^CO

-O-CH ₉ CH = CH-

CH Tiris [2- (N-allyloxyproplonlmldoy 1) -5,5-dloethyl-S-oxo-1-cyclohexenl-yE] -1,3,5-benzene tricart) oxylate

¹ I ⁵²⁴⁶

-O-CH ₀ CH = CH- C, H ₇ 2 Z ί

-O-CH ₀ CH = CH-Z Z

It 12- (N-allyloxybutyrlmidoyl) 5, S-dimethyl-S-oxo-1-cyclohexene l-y £] -2,3,5,6-tetrachloro teirephthalate

Fp. 97-98 ° C

C _{O C} H NO-CH-CH = CH- H C ₀ ,. NO-CH ₀ CH = CH ₀
2 J ^ p ^ Z ZZ 5 \ - ^ ZZ

[2- (N-allyloxypropionimidoyl) -

5, S-dimethyl-S-oxo-1-cyclohexene l-y £ 3-3- [2- (N-allyloxypropionimidoyl) -

SiS-dimethyl-S-oxo-1-cyclohexenyl] -,

oxysulfonyl benzoate

C ₃ H ₇ ^ ^ NO-CH ₂ CH = CH ₂ C ₃ H _7x ^ -

CHg

CHg CH ₃ bis [2- (N-allyloxybutyrimidoyl) -A-methoxycarbonyl-5,5-dimethyl-3-oxo-1-cyclohexen-1-yE,] -terephthalate

23 ⁿ D ¹ I ⁵²¹⁵

ro cn ο

O CD OO CO

CD CD CT) CO

CH- NO-CH-CH = CH- C ₀ H ₁ I NO-CH-CH = CH-2 5x _c ^ · 2 2 2 Sx ^ 2 2

CH ₃ OC

0-C

CH ₃ CH ₃

COOCH-3is [2- (N-allyloxypropionimidoyl) -4-methoxycarbonyl-5,5-d line thy 1-3-oxo-cyclohexene -1-yA] terephthalate

19 η J 1.5282

In the following, the compounds are designated by the number given in Table 1.

As previously mentioned, it has been found that the invention Compounds have superior herbicidal activity. The following is the application of the compounds according to the invention explained in more detail.

The compounds of the invention are particularly effective 7, nr combating Grasunkr ^r iul; s such as one-year] bluegrass (Poa annua L.), water foxtail (Alopecurus aequalis Sobo'l) pinger herb (. Digitaria adscendena Henr), green foxtail (Setaria viridis Beauv) , wild oats (Avena fatua L) etc. and hardly damage broad-leaved crops such as adzuki beans (Phaseolus angularis Wi ^1. Wight) and soybeans (Glycine max Merrill) and sugar beets (Beta vulgaris L.), which are sensitive to phyto-toxicity. The compounds according to the invention are therefore selective herbicides.

It is known that 4-acetoxy-6-methyl-otr-pyrone derivatives with (N-alkoxy or alkenyloxy) acetimidoyl groups herbicides Have properties (DT-OS 22 52 818).

However, in order to completely destroy the mentioned grass weeds, a large amount of these herbicides is required, which is a major disadvantage.

If, on the other hand, the compounds according to the invention are used as herbicides, less than a quarter is used the amount required for the known compounds, complete prevention and eradication of weed growth achieved, i.e. the compounds according to the invention are about four times as effective as the known Links.

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In foliar treatment with the aid of the invention Compounds results in the same amount that leads to the complete annihilation of barnyardgrass and other grassy ones Weeds do not damage broad-leaved plants such as radish (Raphanus sativus L.), Soybeans, garden peas (Pisum sativum I.), spinach (Spinacia oleracea L.), sugar beets and carrots (Daucus carota L.) and when treating the soil before germination, the amount that leads to a complete prevention the germination of barnyardgren does not cause damage to broad-leaved plants.

As mentioned above, safety is related to phytotoxicity extraordinary compared to broad-leaved cover plants great and thus the applicability of the compounds of the invention, i.e. with others In words the application time, the application location and the application concentration variable over a very wide range and the connections can be applied generally.

Another advantage of the compounds according to the invention is that the residual toxicity in the soil or the Plants as well as the acute toxicity for warm-blooded animals and fish is not to be feared, since the compounds are in such a low concentration can be used.

The compounds according to the invention can be used directly for treatment To be applied to the ground before emergence or for post-emergence treatment Leaves of the "plants" or they can be mixed with the soil for pre-emergence treatment. You can on the soil or leaves of plants in amounts of 50 to 1000 g per 10 ares, preferably 50 to 200 g per 10 ares and especially in an amount of about 100 g

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be applied per 1Ö ar.

The invention also relates to liquid or solid herbicides Agents which contain one or more of the compounds according to the invention.

These agents can be prepared by mixing the erfind ungsgem'äßen active ingredient with geigneten carriers in a form such as is commonly employed for Agrοchemikalien _(for example, as wettable powders _f emulsifiable concentrates, dusts, granules, water-soluble powders and aerosols. As solid carriers bentonite, Diatomaceous earth, apatite, gypsum, talc, pyrophyllite, vermiculite, clay and others are used. The liquid carriers used are kerosene, mineral oil, petroleum, solvent naphtha, benzene, xylene, cyclohexane, cyclohexanone, dimethylformamide, alcohol, acetone and others in embossing Means are added in order to obtain a homogeneous stable preparation.

The compounds according to the invention can also be used in admixture with other substances used in agriculture and are used in horticulture and which are compatible with the compounds of the invention, applied together will. Such chemicals can be substances such as those found in plant nutrients, fertilizers, insecticides, Akaricide, Fungicide, Herbicide and Fematocide are known.

As with known herbicides, it is beneficial to those of the invention Use compounds in admixture with a herbicidal compound selected from the following Group:

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N- (3- <chloro -4-methoxyphenyl) -N ', N'-dimethyl urea N- (3,4-dichlorophenyl) -N', N'-dimethylurea N- (3,4-dichlorophenyl) -N'-methoxy-N ¹ -methyl urea 1,3-dimethyl- (3-benzothiazol -2-yl). Urea 1,3-dimethyl-3- (5-methylbenzothiazol -2-yl) urea 1,3 -Diraethyl-3- (5-t-butylbenzothiazol -2-yl) urea 1,3-trimethyl-3- (5-methylbenzothiazol -2-yl) urea 1,3-tcimethyl-3- (5 -ä, thylbenzothiazol.-2-yl) urea 1,3-Dimethyl-3- (5,7-diethylbenzothiazol -2-yl) urea 1,3-lfcimethyl-3- (5,7-dimethylbenzothiazole -2- yl) urea 2-C.hlor '-4, 6-dläthylamino-1,3,5-triazine 2-Qilor -A-ethylamino-o-isopropylamino-l ^ .S-triazine. , 2-chloro - ^ jo-diisopropylamino-LJS ^ triazine, 2-I'Ethylmercapto-4-ethylamino-6-isopropylamino-l, 3,5-tria zin _1, 2-l ^v Iethylmercapto-4,6-diisopropylamino -1, 3,5-triazine., 3-methoxycarbonylaminophenyl-N- (3'-methylphenyl) carbamate, methyl N- (3,4-dichlorophenyl) carbamate, isopropyl N- (3-chlorophenyl) carbamate , '·

S- (4-chlorobenz'yl) -N, N-d ^ .thylthiol carbamate,

• 4 ^f -Witro-2,4-dichloro-diphenyl ether, ■ \

44 ^v Iitro-2,4-6-trichloro-diphenyl ether, 2-methyl-4-chloro-phenoxy acetic acid 2,4-DLclilor-phenoxyacetic acid
3-isopropyl-2,1,3-benzothiadiazine-4-one-2,2-dioxidj and l-phenyl-4-amino-5-chloro-pyridazine,

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The concentration of the active ingredients in the overbicidal agents according to the invention varies depending on the type of preparation and is, for example, in the range from 5 to 80% by weight, preferably 10 to 60% by weight, in the case of wettable powders _; 5 to 70, preferably 20 to wt. -Fo _f in emulsifiable concentrates, and 0.5 to 30, preferably 1 to 10 wt .- $ with dusts.

This becomes a wettable powder or an emulsifiable one Concentrate with water to a special concentration diluted and in TiOrin a liquid suspension or liquid emulsion used to treat the soil or leaves.

A dusting agent is used directly to treat the soil or leaves.

Examples of herbicidal agents according to the invention are given below.

Example 8 Wettable Powder

Parts by weight

Compound No. 2 '50

Diatomaceous earth 21

Sodium alkyl sulfate 8

Talc. 21

These substances were mixed homogeneously and ground to a finely divided powder. A wettable powder containing 50 % active ingredient was obtained. In practical use, it was diluted with water to a certain concentration and sprayed as a suspension.

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Example 9 Emulsifiable Concentrate

Parts by weight

Connection ur. 1 40

Xylene 35

Dimethylformamide 15

Polyoxyethylene phenyl ether 10

The substances were mixed and dissolved.

An emulsifiable concentrate was obtained containing

40% by weight active ingredient. In practical application was it diluted with water to a certain concentration

and sprayed as an emulsion.

Example 10 granules

Parts by weight

Compound No. 3 7

Talc 38

Bentonite 1O

Tone 38

Sodium alkyl sulfate 7

These substances were mixed homogeneously and ground into a fine powder. Granules with a particle size in the range from 0.5 to 1.0 mm were produced from the powder with the aid of a granulator. Granules containing 7 μl of active ingredient were obtained. These granules were applied directly in the practical application.

The superior herbicidal activity of the compounds according to the invention can be seen from the following experiments.

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2601U7

7ersach 1

Pre-emergence treatment (treatment of the soil under greenhouse conditions).

About 60 seeds of chicken millet were in a pot

ρ sown with a surface of 60 cm and light-fc with

Earth covered. V / ater was poured into the pot until the surface was wet.

10 ml of an aqueous emulsion which has been prepared by diluting an emulsifiable concentrate with Water of a specific concentration was sprayed on the pot. The pots were kept in the greenhouse and watered daily to keep the water level constant. Three weeks after spraying, the grade became the destruction of the plants and rated on a 0 to 5 scale according to the following meaning.

0: no effect

1: Parts of the plants slightly damaged

2: plants slightly damaged

3: Plants moderately damaged

4: Plants badly damaged

5: Plants completely killed or no germination

The results given in Table 2 were obtained

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60 9 8 31/0963

Table 2

Connection no. Application rate (g / 10 Ar) 60 30th 0 1 125 5 5 2 5 '5 5 3 5 5 5 4th 5 5 5 5 5 5 5 6th 5 5 5 9 '5 5 5 18th 5. 5 5 Comparison connection
0-CO-CH ₃ 5 • 3 1 not treated . 5

* Offenlegungsschrift 2252818 Experiment 2

Post-emergence treatment (treatment of leaves under greenhouse conditions)

About 50 seeds of chicken millet were in a pot with sown on a surface of 60 cm and lightly covered with earth. The pot was raised to a height of approximately 3 cm above the surface of the. Earth filled with water after the plants had reached a leaf.

An aqueous solution prepared by diluting an emulsifiable concentrate with water to one special concentration. was sprayed onto the pot. the

609831/0963

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2601U7

Pots - were kept in the greenhouse and watered daily added to keep the water level constant. Two weeks after the spraying, the degree of destruction was determined of the test plants observed and rated according to the 0-5 scale given above. One received the results given in Table 3 below.

Table 3

Application rate (g / 10 Ar) ' 125 60 Connection no. -. 250 5. 3 2 5 5 5 3 5 5 5 5 5
«, 5 5 6th 5 5 5 9 5 5 5 18th 5 4th 2 Comparison connection
O-CO-CH
JL _r * NOC H 5 0 ! not treated

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609831/0963 COPY

Attempt 5

Treatment before emergence.

Pingerwort seeds were placed in a pot with a Area of 100 cm given. An aqueous emulsion made by diluting an emulsifiable one Concentrate with water to a special concentration was on the surface of the soil before emergence sprayed on. The pots were kept in the greenhouse. 21 days after the spraying, the degree of destruction was determined of the test plants observed and rated according to the 0-5 scale given above. Those given in Table 4 below were obtained Results:

Table 4

Application amount (g / 1.0 -Ar) 125 0 60 ■ j 30th - Connection ur. 250 5 5 3 1 5 5 4th 3 2 5 5 5 4th 3 5 5 4th 3 4th 5 5 5 5 5 5 5 5 5 6th 5 5 5 5 9 5 Comparison connection
O-COCH 3 1 0 rrC ² " ⁵ 5 CH, 0 not treated

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609831/0963

Attempt 4

Post-emergence treatment (treatment of the leaves)

There were seeds of weeds in a pot with a

ρ
Sown area of 100 cm. After the plants reached 2 Ms 4 leaves, an aqueous emulsion prepared by diluting an emulsifiable concentrate with water to a specific concentration was sprayed on the leaves of the test plants in an amount of 100 l / 10 ar. The plants were kept in the greenhouse.

21 days after the spraying, the degree of destruction of the test plants was observed and corresponding to that rated O - 5 scale given above. You got the results given in table 5:

Table 5

Application rate • * (g / 10 Ar) - Connection no. 200 100 50 2 5 5 4th 3 5 5 4th 4th 5 5 4th 5 5 5 4th 6th 5 5 4th 9 5 5 4th 18th 5 4th Comparison connection
0-COCH ₃
^ NOC ₂ H ₅ 4th 2 1 '* not treated 0

PATENT CLAIMS 609831/0963

Claims (10)

Claims in which B ... a lower alkyl group with up to 6 carbon atoms, IL, a lower alkyl group with up to 6 carbon atoms or a lower alkenyl group with up to 6 carbon atoms, R ^ a hydrogen atom or a lower alkoxy carbonyl group with up to 6 carbon atoms , R is an aliphatic or aromatic ester residue of a di- or tribasic acid and η is 2 or 3 . 2. Compounds according to claim 1, gekennzeioh net by the, formula R N-OR ₂ in which R. is an ethyl or propyl group, R _{2 is} an ethyl or allyl group, R ^ is a hydrogen atom or a methoxycarbonyl group and R is an aliphatic or aromatic ester residue of a dibasic acid. 609831/0963 2601U7 3. Compounds according to claim 1 or 2, g e k e η η draws by the formula ₁ N-OR ₂ o-cc R ₁ N-OR ₀ ¹ V ² -CO- CH-CH ₃ 1 CH3 CH ₃ i ⁿ the R .. Äthyloder a propyl group, R ₂ represents a Äthyloder allyl group and R ~ is a hydrogen atom or a methoxycarbonyl group. 4. A compound according to claim 1, characterized ne t by the formula 5. Compound according to claim 1, characterized by the formula O-CO (O) CO-O. . CH ₃ CH ₃ 6, connection according to claim! by the formula C ₀ H ^. ^ NO-CH ₀ CIl-CH ₀ C ₁ H., NO-CH ₀ CH = CH ₀ 3 7 \ // 2 2 3 7 \ ^ 2 2 0-CO-fvV-CO-O CH ₃ CH ₃ CH ₃ CH ₃ 609831/0963 7. A compound according to claim 1, characterized by the formula CH ₃ OCO N-O-CH CH = CH, VV Lcooch_ CH ₃ CH ₃ 8th'. A compound according to claim 1 characterized by the formula ΟγΛγΌ-CO- / \ _ ._ ^CH 3 CH ₃ CH ₀ CH 9. Process for the preparation of the compounds according to Claims 1 to 8, characterized in that that one is a compound of the formula CH ₃ CH ₃ λ in the R., Rp, R ^, and η the meaning given above have, reacted with a compound of the formula R (Cl) ■ in which R and η have the meaning given above in Presence of alkali. 10. ' Herbicidal agents containing at least one Compound according to Claims 1 to 8, optionally together with a customary inert carrier and / or surfactants. 609831/0963