NL7906019A - CARBAMIC ACID PHENYL ESTERS, METHOD FOR PREPARING THE SAME AND HERBICIDES CONTAINING THESE COMPOUNDS. - Google Patents

Description

* s r f _ '__! i> T0_8198_

Schering Aktiengesellschaft

Berlin and Bergkamen, Federal Republic of Germany.

Carbamic acid phenyl esters, process for their preparation, as well as herbicides containing these compounds.

The invention relates to new carbamic acid phenyl esters, to a method of preparing these compounds, and to a method of preparing herbicides containing one or more of these compounds.

5 The Belgian patent specification 606.293 already contains the. use of 3- (carbamoyloxy) anilides as herbicides is known.

The object of the present invention is to provide new active compounds with better herbicidal properties. This object is achieved according to the invention by an agent, characterized in that it contains at least one compound of the general formula 1, in which: C 1 -C 8 -alkoxy-C 1 -C 2 -alkyl, di-C'-Cg -alkoxy-C 1 -C 8 -alkyl, cyano-C 1 -C 8 -alkyl, halogen-C 1 -C 8 -alkyl, phenyl-C 1 -C 1 -alkyl, 1,3-dioxolan-2-yl-methyl, 2 methyl-1,3-dioxolan-4-yl-methyl, 2,2-15 dimethyl-1,3-dioxolan-4-yl-methyl or aminocarbonylmethyl,

Rg represents phenyl, phenyl and C 1 -C 8 alkyl, C 1 -C 8 alkenyl, cyclopropyl or tri-chloromethyl substituted by halogen and / or methyl and / or methoxy, or 20 R 1 methyl or ethyl, R ^ α cyano-benzyl or 1-cyano-2-phenylethyl and Rg represent ethyl.

The compounds of the invention are surprisingly superior to the anilides known from the above prior art in terms of their herbicidal activity and thus represent an enrichment of the prior art in this field.

The herbicidal activity of these compounds is directed against a large number of undesirable plant species and not against 7906019 '2 - P * cultivated plants, against which they exhibit a pronounced selectivity spectrum.

If very good control are plant species can e.g. the following are mentioned: 5 Gramineae

Festuca sp .., Alopecurus sp., Agrostis sp., Echinochloa, Setaria so ,, Sorghum sp., Poa sp., Lolium sp., Arhhenaterum sp., Phalaris sp., Phleum sp., Eleusine sp., Bromus sp. , Hordeum sp. and others. Cyperaceae 10 Cyperus sp. and others.

Liliaceae

Allium sp. and others.

Amaranthaceae Amaranthus sp. and others.

15 Boraginaceae

Anchusa sp., Amsinckia sp., Myosotis sp. and others.

Caryophylaceae

Stellaria sp., Spergula sp., Cerastium sp. and others.

Chenopodiaceae 20 Chenopodium sp., Salsola kali, Atriplex sp., Eochia sp, and others. Convolvulac eae Ipomea sp. and others.

Compositae

Ambrosia sp., Lactuca sp., Senecio sp., Xanthium sp., Galinsoga 25 sp., Centaurea sp., Matricaria sp., Helianthus sp., Chrysanthemum sp., Cichorium intybus and others.

Cruciferae

Brassica sp., Cheiranthus cheiri., Capsella sp., Thlaspi sp., Sinapis sp. and others.

30 Euphorbiaceae Euphorbia.

Labiatae

Lamium sp., Galeopsis sp. and others.

Leguminosae 35 Medicago sp., Trifolium sp., Vicia sp., Cassia sp. and others.

7906019 ... * 3 <3.

Malvaceae

Abutilon theophrasti, Sida sp., Hibiscus sp., Anoda and others.

Papaveraeeae

Eapaver sp., Eseholtzia and others.

Polygonaceae

Polygonum sp. and others.

Portulacaceae Portulaca sp. and others.

Rubiaceae 10 Galium sp., Richardia sp. and others.

Ranunculaceae

Delphinium sp., Adonis sp. and others.

Scrophulariaceae

Lip aria sp. * Digitalis sp., Veronica sp. and others.

15 Solanaceae

Datura sp., Solanum sp., Physalis sp. and others.

Urticaceae

Urtica sp. and others.

Umbelliferae 20 Daucus carota and others.

As a rule, amounts of 1 - 5 hg active compound / ha are used to control seed weed species.

The application against these plant species can take place before emerging or after emerging. A particular advantage here is that the compounds according to the invention have particularly high tolerances in farmland cultures, in particular with respect to cotton, potatoes, frame, soy and sugar beet.

The compounds of the invention can be used either alone or intermixed or mixed with other active compounds. If desired, other defoliators, plant protection agents or pest control agents may be added according to the desired purpose.

If a broadening of the activity spectrum is envisaged, other herbicides can also be added.

7906019 r * k "

For example, e.g. suitable herbicidal mixing components: active compounds from the group of triazines, arino triazoles, anilides, diazines, uraciles, aliphatic carboxylic acids and halocarboxylic acids, substituted benzoic acids and aryloxycarboxylic acids, hydrazides, amides, nitriles, esters of the aforementioned carboxylic acids, Carbamic acid and thiocarbamic acid esters, urea derivatives, 2,3,6-trichlorobenzyl oxypropanil, thiocyane-containing agents and other additives.

For example, under "other additives", also to be understood: non-phytotoxic additives, which can effect a synergistic increase in the effect with herbicides, such as wetting agents, emulsifiers, solvents and oily additives.

It is recommended that the active compounds according to the invention or the mixtures thereof be in the form of preparations, such as powders, litters, granulates, solutions, emulsions or suspensions with the addition of liquid and / or solid carriers or diluents and optionally of. wetting, bonding, emulsifying and / or dispersing agents.

Suitable liquid carriers are e.g. water, aliphatic and aromatic hydrocarbons, such as benzene, toluene, xylene, cyclohexanone, isophorone, dimethyl sulfoxide, dimethyl formamide and further mineral oil fractions.

Suitable solid carriers are: mineral earths, e.g. tonsil, silica gel, talc, kaolin, attaclay, limestone, silica and vegetable products, e.g. flours.

As surface active compounds, e.g. are mentioned: calcium lignin sulfonate, polyoxyethylene alkyl phenol ethers, naphthalene sulfonic acids and their salts, phenol sulfonic acids and their salts, formaldehyde condensation products, fatty alcohol sulfates, and substituted benzene sulfonic acids and salts thereof.

The content of active compound or active compounds in the different preparations can vary within wide limits. For example, the agents, e.g. about 10 - 80 wt.% action compounds, about 90 - 20 wt. liquid or solid carriers, 7906019-5 and optionally at most 20 wt. surfactants.

The application of the agents can take place in the usual manner a h.v. amounts of approximately 100 - 1000 liters / ha to be sprayed with water as a carrier. The use of the mid-5 parts in the so-called "low-volume" and "ultra-low-volume" process is just as possible as their use in the form of so-called micro-granulates.

The new compounds according to the invention can be prepared according to methods known for analogous compounds.

According to the invention, the new compounds are e.g. prepared by: compounds of the general formula 2 in the presence of organic bases, such as e.g. pyridine, or in the form of alkali salts, e.g. the sodium or potassium salt, either to be reacted with compounds of the general formula 3 or to add inorganic or organic bases, e.g. sodium hydroxide or dimethylaniline, with phosgene first converting into the corresponding chloroformic esters of the general formula k, then these esters then with compounds of the general formula 5 in the presence of bases, such as e.g. potassium carbonate, and the products obtained thereby are isolated in a manner known per se, in which formulas, R 1 and R 2, have the above meanings.

As a solvent for these reactions, e.g. suitable: ethyl acetate, acetonitrile, hexane, benzene, toluene, methylene chloride, carbon tetrachloride, tetrahydrofuran, dimethylformamide and other agents inert to the reactants.

In all reactions, the conversion takes place at temperatures between 0 ° C and the respective boiling point of the solvent.

The hydroxy anilides to be used as starting compounds are obtained in a manner known per se by reacting the corresponding acid chlorides with m-amino phenol.

The invention is illustrated by the following examples 7906019-6.

# 5 = * "images explained in more detail.

Example I

N- (2,2-Diethoxyethyl) -carbanilzunr- [3- (2,2-dimethylvalerylanr.no) -phenyl] ester 5 In a solution of 20.9 g (0.1 mol) H- (2 2-diethoxyethyl) -aniline in 50 ml of ethyl acetate while stirring and cooling to. 10 - 15 ° C a solution of 28.3 g (0.1 mol) chloroformic acid 3- (2,2-dimethylvalerylamino) phenyl ester and at the same time a solution of 13.8 g (0.1 mol) potassium carbonate in J0 ml water dripped.

10 Stirred at room temperature for 30 minutes, then the organic phase separated, diluted with a little ethyl acetate, washed at 0 ° C with dilute hydrochloric acid and sodium chloride solution, dried with magnesium sulfate and the solvent distilled off under reduced pressure. was recrystallized from ethyl acetate / pentane.

Yield: 36 g = 19% *

Melting point: 88 - 89 ° C.

Example II

H- (2-cyanoethyl) -3-methylcarbanilic acid [3- (3-chloromethylcarbonylamino) -20 phenyl] ester

Dropped 31.7 g of chloroformic acid 3- (3-chloromethylcarbonylamino) -phenyl ester, taken up in 100 ml of acetonitrile, in a solution of 16.0 g of N- (2-cyanoethyl) -3-methylaniline in 100 ml of acetonitrile. Then add 12.1 g of 25 N, H-dimethylaniline to the reaction mixture. A temperature increase to h6 ° C occurred during this. The reaction mixture was boiled for an additional 10 minutes, cooled, placed in 500 ml of ice water with stirring, the precipitated substance filtered off and recrystallized from isopropanol.

Yield: 31.5 g = 72 $.

Melting point: 118 ° C.

Example III

H-cyanomethylcarbonic acid- [3- (ter-butylcarbonylamino) -phenyl] ester

25.57 g of hydrochloric acid [3- (tert-butylcar-35-bonylamino) -phenyl] -ester-ester are added to a solution of 13.2 g of H-cyanomethylaniline in 150 ml of acetonitrile, followed by stirring 79 0 6 0 1 9 7 - 12.1 g of Ν, Ν-dimethylaniline was added dropwise and the mixture was boiled for an additional 15 minutes. After cooling, the mixture was placed in 1 L of ice water with stirring, the separating substance was suctioned off and recrystallized from a little acetonitrile after drying under reduced pressure.

Yield: 2k, 0g = 68%.

Melting point: 173 ° C.

Example 17 N- (2-cyanoethyl) -carbanilic acid- [3- (cyelopropylcarbonylamino) -phenyl] -10 ester

29.2 g of N- (2-cyanoethyl) -aniline were dissolved in 200 ml of acetonitrile and 23.97 g of chloroformic acid [3- (cyelopropylcarbonylamino) -phenyl] -ester were added with stirring, the temperature of the solution rose to 35 ° C. After standing overnight, the solvent was distilled off under reduced pressure, the remaining oily residue treated with water, the water decanted off and the oil crystallized using a mixture of isopropyl ether and isopropanol (1: 1). The crystallizate was then recrystallized from isopropanol.

Yield: 16.59 g = k8%.

Melting point: 11 + 2 ° C.

Example V

N-cy a n.n with hyl-3-met h: / ~ lc arb anil acid Γ3- (propionylamino) -phenyl] -ester The preparation prepared from 6h, kg (0.39 mol) of propionic acid-3-hydroxy-anilide potassium salt was taken up in 300 ml of acetonitrile. When a solution of 81 k g (0.39 mol) of N-cyanomethyl-N- (3-methylphenyl) -carbamoyl chloride in 250 ml of acetonitrile was added dropwise over 5 minutes with stirring, the temperature rose from 28 to V} ° C. It was then refluxed for 30 minutes. After evaporation under reduced pressure, it was dissolved in ethyl acetate and water, washed with a small amount of dilute sodium hydroxide at 0 ° C, dried with magnesium sulfate and evaporated under reduced pressure. The initially oily residue crystallized from ether.

Yield: 80 µg = 6λ%.

35 Melting point: 97 - 99 ° C7906019 tr * a

The following compounds according to the invention could be prepared in an analogous manner:

Name of the connection_Physical constant

N- (2,2-dimethoxyethyl) -carbanilic acid-5 [3- (propionylamino) -phenyl ester Mp: 7 * 1-73 C

N-Cyanomethylcarbanilic acid (3-pro

pionylaminophenyl) ester Mp: 130 C

N- (2-Cyanoethyl) -3-methylcarbanilic acid-

(3-propionylaminophenyl) ester Mp: 11 * 9-151 C

10 N- (2-Methoxyethyl) -carbanilic acid- [3-propylamino-phenyl] -ester Mp: 71-72 0 N- (2-Cyanoethyl) -1 * -methylcarbanilic acid-

[3-prapionylamino-phenyl] ester Mp: 121 * -126 ° C

N ~ (2-Cyanoethyl) -2-methylcarbanilic acid-15 (3-propionylaminophenyl) ester Mp: 120-122 ° C

N- (2-Methoxyethyl) -3-methylcarbanil-

acid (3-propionylaminophenyl) ester Mp: 82-81rC

N- (2,2-Dimetho: xyethyl) -1 * -methylcarbanil- 2q acid- [3- (propibnylami.no) -phenyl] -ester el 1: 1,531 * 3 20 H- (2,2-Dimethoxyethyl) -3-methylcarbanilic acid [3- (propionylamino) -phenyl] -ester n ^: 1,51 * 05 N- (2-bromomethyl) -carbanilic acid-C3-

(propionylamino) -phenyl] ester Mp: 86-87 ° C

N- (2-Ethoxyethyl) -carbanilic acid- [3—

(Propionylamino) -phenyl] ester Mp: 83-81 * uC

N- (2-Cyanoethyl) -carbanilic acid- [3-

(propionylamino) phenyl] ester Mp: 126-128 ° C

N- (2,2-Dimethoxyethyl-2-methylearbanil-

acid [3- (propionylamino) -phenyl] ester Mp: 105-107 ° C

30 N- (1-Cyano-2-phenyl-ethyl) -N-methyl-

carbamic acid [3- (propionylamino) -phenyl] ester Mp .: 10l + ° C

N- (a-Cyanobenzyl) -N-ethyl-carbamine-

acid [3- (propionylamino) -phenyl] ester Mp: 6 ° C

N- (2-Cyanoethyl) -3-methylcarbanil—

Acid [3- (tert-butylcarbonylamino) phenyl] ester Mp: 122 ° C

N- (2-Cyanoethyl) -carbanilic acid- [3-

(tert-butyl arbonylamino) -phenyl] ester Mp .: 118 ° C

N- (1,3-Dioxolan-2-yl-methyl) -carbanilic acid- [3- (propionylamino) -

1 * 0 phenyl] ester Mp .: 98-99 ° C

3-Methoxy-N- (2-methoxyethyl) -carbanilic acid- [3- (propionylamino) -phenyl] -ester nD: 1 * 561.1 * 7906019 (Tervolg)

Name of the Terbinding______Physical constant «* '9 N- (U-Methyl-1,3- <iioxolan-2-yl-methyl) -carhanilic acid- [3- (propionylamino) -: phenyl ester: 1.5559 5 N-Cyanomethylcarbanilic acid- [3- (2,2-

dimethylvalerylamino} -phenyl] ester Mp: 152-153 ° C

N- (2-Cyanoethyl) -carhanilic acid- [3-

C 2,2-dmethylTalerylamino) -phenyl] -est er 9α .: 93-95 ° C

N- (2-Cyanoethyl) -carbanilic acid- [3-

10 (21-methylpropionylamino) -phenyl] ester Mp: 136-137 ° C

N- (2-Chloroethyl) -carbanilic acid- [3-

(2,2-dimethylvalerylamino) -t enyl] -est er Mp .: 101-102.5 ° C

N- (2-Chloroethyl) -carhanilic acid- [3- (pro—

pionylamino} -phenyl] ester Juice, 107-109 ° C

15 JT- (2-Phenylethyl) -carhanilic acid- [3-

(propionylamino) -phenyl] ester Sap .: g ^ -gh ° C

(— (2-Cyanoethyl} -carbanilic acid- [3-

(crotonoylamino) -phenyl ester Sap .: 117-119 ° C

N- (2-Chloroethyl) -carhanilic acid- [3-

20 (crotonoylamino) phenyl] ester Mp: 131-133 ° C

N- (2,2-Dimethoxyethyl) -carbanilic acid-

[3- (2,2-dimethylvalerylamino] -phenyl] ester Mp: 77-79 ° C

N- (Minocarhonylmethyl) -carbanilic acid-

[3- (cyclopropylcarhonylamino) -phenyl] ester Mp: 197 ° C

25 N- (2-Aminocarhonylethyl) -carhanilic acid-

[3- (cyclopropylcarhonylamino] -phenyl] ester Mp: 166 ° C

N- (2-Cyanoethyl) -3-methylcarhanilzunr-

[3- (cyclopropylcarhonylamino) -phenyl] ester Mp: 175 ° C

N-Cyanomethylcarhanilic acid- [3- (trichloro-30-methylcarhonylamino) phenyl] ester Mp .: 102 ° C

N- (2-Cyanoethyl] -carhanilic acid- [3- (tri-

chloromethylcarhonylamino) -phenyl] ester Sap .: 137 ° C

N- (2-Methoxyethyl) -carhanilic acid- [3- (tert-hutylcarhonylamino) -phenyl] -ester n ^: 1,5509 35 N- (2-Methoxyethyl) -3Huethozycarhanilic acid- [3- (tert-hutylcarhonylamxno) -phenyl ] -ester n ^: 1.51 * 82 N- (2-Methoxyethyl) -carhanilic acid- [3-

cyclopropylearhonylamino] -phenyl] ester Mp: 133 ° C

N- (2-Methoxyethyl) -carhanilic acid- [3-20

1 * 0 (trichloromethylcarhonylamino) phenyl] ester, 1.55oV

N- (2-Methoxyethyl] -3-with hoxycarh anil acid-

[3- (trichloomet hylcarb onylamino) phenyl] ester Mp .: 135 ° C

79 0 60 1 9 10 • (Continued)

Hmïii of the compound__. Physical constant N- (2,2-Dimethyl-1,3-dioBcolane-1f ** yl-methyl) -carbanilic acid- [3- (2,2-dimethyl-

valerylami.no-phenyl] -ester Snip .: 100-102 C

5 N- (2-Ethoxyethyl) -carbanilic acid- [3-

(cyclopropylcarbonylamino) -phenyl] ester Sap .: 109 C

N-Cyanomethyl-3-chlorocarbanilic acid- [3-

(trichloromethylcarbonylamino) phenyl] ester Snip .: 162 C

N- (2,2-Dimethaxyethyl) -3-methyl- 1,0-carbanilic acid- [3- (tert-butyl-carbonilamino) -phenyl] -ester viscous oil N- (2-Hydroxyethyl) -carbanilic acid-

[3- (cyclopropylcarbonylamino) -phenyl] ester Mp: 116-11T ° C

I- (2-Methoxyethyl) -h-fluorocarbanil-15 acid- [3- (cyclopropylcarbonylamino) -

phenyl] ester monkey: T03-105 ° C

U- (2-Etboxyethyl) -ij-fluorocarbanilzunr - ('3-

(cyclopropylcarbonylamino) -phenyl) ester Mp: 77-79 ° C

The compounds of the invention are colorless and odorless crystalline or oily substances which are readily soluble in acetone, dimethylformamide, isophorone, cyclohexanone, tetrahydrofuran and dimethyl sulfoxide.

The preparation of some starting compounds is explained in more detail below.

A) 2,2-Dimethylvaleric acid-3-hydroxyanilide

In a solution of 327 g (3 mol) m-aminophenol in. about 1 liter of ethyl acetate was added dropwise, after adding 100 ml of water and your g of magnesium oxide, with stirring, g / g (3 mol) of 2,2-dimethyl-valeric acid chloride, keeping the temperature at 10-30 ° C by cooling. The mixture was stirred for 1 hour at room temperature. Afterwards, 100 ml of concentrated hydrochloric acid were added dropwise at 0-5 ° C and stirred for 10 minutes. The organic phase was then separated, washed with sodium chloride solution to neutral and dried with magnesium sulfate. The ethyl acetate ester was partially distilled off and pentane was added to the residue, after which the reaction product crystallized out.

Yield: 550 g = 83¾.

Melting point: 155-156 ° C.

7906019 it π

In an analogous manner were obtained: propionic acid 3-hydr cocyanilide, melting point: 183-185 ° C; 2-methylpropionic acid 3-hydroxyanilide, melting point: 180 ° C; crotonic acid 3-hydroxyanilide, melting point: 158 DEG-159 DEG C. b) Chloroformic acid-3- (propionylamino) -phenyl ester

To a solution of 177 ml of phosphea in 700 ml of ethyl acetate was added 292 g (1.77 mol) of propionic acid 3-hydroxyanilide.

Then, while stirring and cooling to 10-15 ° C, a solution of 225 ml (1.77 mol) of ff, ff-dimethylaniline in 300 ml of ethyl 10 acetate was added dropwise. The mixture was then stirred at 50 ° C for 30 minutes. The solution cooled to 10 ° C was poured on ice, stirred for about 10 minutes, the organic phase separated, washed with brine, dried with magnesium sulfate and evaporated under reduced pressure. The residue crystallized after adding 600 ml of pentane.

Yield: 327g * 81 $.

Melting point: 72-73 ° C.

In an analogous manner were obtained: chloroformic acid 3- (2-methylpropionylamino) phenyl ester, melting point 69-71 69 chloroformic acid 3- (crotonoylamino) phenyl ester, n: 1.5327; ® 20 20 chloromereic acid 3- (2,2-dimethyl hylvaler oylajnino) phenyl ester, n: 1.5273.

e) Chloroformic acid [3- (eyelopropylcarbonylamino) -phenyl] ester

100 ml of phosgene was condensed at -20 ° C and then taken up in 1 liter of ethyl acetate, after which it was added 0 ° C with stirring 177 µl of cyclopropanecarboxylic acid 3-hydroxy anilide, mp 18h ° C. 121 g of β-dimethylaniline were then added dropwise to this reaction mixture with continued cooling. It was then stirred at 40 [deg.] C. for an additional 1 hour, the excess phosgene expelled through a stream of nitrogen gas, the mixture cooled to room temperature and the. ethyl acetate phase extracted twice with 250 ml of ice water, after separating the organic phase, it was dried with magnesium sulfate, the solvent was distilled off under reduced pressure and the resulting residue was crystallized by adding petroleum ether. In this way, 207 g (86 $) of the above substance with a melting point of 91 ° C were obtained.

In an analogous manner were prepared: 7906019,12 chloroformic acid [3- (tert-butylcarbonylamino) phenyl] ester, mp 75 ° C; chloroformic acid [3 - ((trichloromethylcarbonylamino) phenyl] ester, Na: 1.5786.

The following examples serve to illustrate the uses and superior herbicidal activity of the compounds of the invention.

Example VI

In a greenhouse, the compounds according to the invention mentioned in the table below were dissolved in 500 l water / ha, in an amount of 5 hg • active compound / ha, after emergence on Solanum and Bras si ca .

Brie weeks after treatment, the treatment result was assessed, with: 15 0 = no effect, and k = destruction of the plants. As can be seen from the table, destruction of the test plants was generally achieved.

7906019 13 (Η Ο

CQ

cd 0 cd m iii I H co cn! I I.

I _I sl i_i 1 — r fj r-i H * a & i§iii'sh | j -¾¾

, oH.HddNCdOCoO SS

m S & g § 1 g d f ti S S i i * II I d s, d d § „s ï g ΐ a ώ λ s ® H 5 Q. ς * U> 5? Ö Ö, ΩΦΗι — i H i — I 1—1 i '-t * CJ π • S «^ Ύ S-p cA | n J *. S -s έ * | g L g | II i llv ij I5 3? is s s § 15 sj §j | s 1 II A 31 é Άί gl Μ JV fV dS 3 8 ^? i t 3 bL —j 5 bs I bs I + j ^ ή i η I · η I I "

¢, VA 3 Ρζ, N J? A jdrA CD Ö ΙΟ IO Sn gr ~ i Q r — i CVI O

10 HS Η 15 S -H 1¾¾ ÏS f <£ H-S H-S 1¾ 'SU 1¾ h | g || -a h fv i „? I? s 7J. ^^ s as s s a s # | § + sq-i §dj ro, α <u ft oj <pqO -p d -p 'i V ^ i * A V? V · $ si hC <U I P Ρ l O ft II t’Ss. ^ Sp? AA r-i A A A sL d 3 si? S! H.S S S O's df? 11 IS 11 i § I § t § 1-3> J | ^ || §A II |. | ll || || f | 11 || 11 s il 5 & S & -S & si s § i &, i &, §1 & | | 1 ||

0-5¾¾¾ rfo SO) g * S b λ · η ΐγ -H «Od ^ ö ddpT

._j <* d λ, 5 «r-ι bd <Li d d d ö -p Pi Hi Hi? h Π G lS. λλ friio St 5L 8, S t £> o S * ο ϊ ο i m ion ^ o -p o ho i on * 3 rvi 3 S ^ -L O rt -Is. Ο · Η Ο · Η 2 OJ · —1 CVJ 1 — I PQ · Η (¾ · Η O »rl CVJ 1—1 .S ° ia, 9 SS ^ TI ft I ft 7 ft * I" II ft I ft i ft "i

jd 0J & i> s fi W ^ «C cup CUO CU '-' CJB

I I * 31 Xa 31 Xê X * ia a g a is is as a g 7906019 - .. Ill ·, ΐ ~.

1? ο t 2> * —- § _d- -d · .d- -d- -d- -d · -d- -d ~ - = f '-d · -d' - = r 3 to a? o JQ J · J "J · J · -d *» d "'-d- J" —f .df · «2 · H” to 2 (¾

I 1 I I

I H I --- I CM p

CO I 2 .H P Η p Η I OJ I «P

1 1 (DO) Ö JJ · Η 0 S'— '«I <—1 CM H

. I I 2 + 3 2 + 3 2 + 3, 20, f CM OJ IH γ. γ b £ 2 HI -h to n to 2 cn +3 2 | 2 '-'2' ~ 'PP> s> Pl

2 3 b, - So 2 4), 0 4) 2 -H CM 2 12 12 3 2 00 4) CO

• H 5 J? O 2 I 2 I P I a g »-P CO +3 CO +3 3 4; 1-3 + 3 1-1

Η N +3 ö H 1—1 U 1 — I cö I — I I «J OJ CO 1—1 CO I — I CO N Η I CO I

CH Ο) <ri d H IHOHHH W4) 14) 14) HI p 2 2 • η · η 2 S S aj> j 'S IS S S II P 1 h 1 "d 0 3 1 §

> Ö4) I 3 ÜÖHÖ '-'P! I 2.00 c — i dn dn Ö O SCS

+: a3 +3 a Η I 2 S 2 -H 2 OJ O uh ίΗ -3H ιί β. NHN

. H H w IS Η 4π Λ l ·) S H I cp, 1 E? i ί f? ? a H S H

2 2 4) --- ö Si -PI iC I 2 14 H 2 H 53 H 2 b I - 9 'd aj I HO rC'—' 4) —- +3 - cö 3 3 4) H 4) * H 4) 3 9 2 2 2 4)

4) O r — 1 S Ή +30 SO 4) 0 COO 3 4+ 2 4+ 2 4- <Ο H £ 4h 2 -P

t3hh λ 1¾ 0 2 I 2 s 2 η h ^ 'S' S A "b -P · £ S

Ss-po IHH-hM-HOS H'- ', Α —'-' Ει fn - - fj 4) w yes 2 2 p ö§ d 2 3 2 3 2 d iT oj - o S 1 ö + jojift i 2 I 2, 2 2 o + j ö 2 cd ö ..ο 2 S Η οβ οι — i

4) 4) 4+ H '- H CM H +3 Η · Η 4) cd · Η O · Η α · Η H rf I · Η I H

MSI SI HSISOS-O'-T>? § 1 § 1 I if,> -Cl j

Hl «—- 0 co S 2 2 2 S 2 II P cd 'co - co 4) H H. 2 H 2 O CO O 4) 1—1 NO Cd OIO CO CO CÖ Η Η H Η H SS S Η. 2 t> 1 2 4+ I 2 h 3 ή cvi · η · ί — i üS SS SS ιί j) π S, 2 4-i

Η · η IP H) ft Η Pi '—- ft> I H 4 d 4 Λ P 3d -P P -PI

Ö SS Ol 3 P Η Ο Ο Ο I Ο IP p S 4) +3 4) +3 Ο Λ 4) 4) d) 4) -— · 4) B § 12 4) I p HP aph 2 4) pH 2H 2 · 3 if, § 3d 3 2 M +3 H ÖN + 3 Cft Oft IP <£, 3 + 5- ^ 2 22 2 ft: 2 H 2 2 23 2 4) S 2 4) 2 2 - 'H * - 'S'-' Λ N CQ 4) f> 2> 2 Ο · Η T) O t Ο · Η • H§fl224) 2lOIHIHH4) iH2H 22 PJ dd.d§ "2 2 Ο>» · Η IS co I CO O CO 4) -Η I 2 SSSS ft I CM £ S £ 2 2 2 Η OSI — 1 01—1 CO1 — I r2 1—3 J3 2 I-! O> 2 Ο H CM _ «S > d.

• H cd 2 1 2 H I I ·> I +3 I I 2 H 3 +3 I +3 | S "CM p 1 + 3 IS

H S o P · H S a P P J P η · H S S o CM O OJ A CM γ 2 CM 2 CM 2

tj O 2 -__ 2 2 - 2 —- 2 S 2 '-' 2 2 OS - 'S v—' + 3-. - I +3 '- S - O

S é “i Jk 3 l § Λ § ώ §ί ά3 A« is «È" s -kS AΆ 790 6 0 1 9 β 15 60 Η £ α5> § J · -3- -3 "-3- -3 - -3- J-.3--3 · - = * · * Η Ο

CQ

ai Ο £ J- -3- -3r ^ -3--3-. * ^ · * “· * ^ tö pq /

I I S

+3 0 i 3 k ° u'rt -p Sr-π-ΡΛ r — i $ ,, Λ. A £

• HfO CO <_I b3 <U 00 H -p? -L 3 3 fOM ^ OJ IO

<rt i_t t — JIH CU l — J r * »v - ** <D CSj <U —1 <U -P" P Η 5) d I 1 Sh -HI I Ö I -p, Q <Η I - P '3 3 ^ .2 ih L 3¾ i fc co η ϊ I Ml® g IJ.

b. d 0) 35) 35) 30 3 Vi 1—1 ®) 3 '-' 3 ®J ΟΠ I C5I.

L §2 30 31 ΙΓϋΟ 31 '—rn HO XM

.¾ δΙί δΐ-Ηβ f.H urj I s «<3 Λς> * d.g 2 £ 2

"3A-gA§A?, 5 · 3 · | 15 | i g & il II || S

• fi & l & s & Ïis fin a "? I & it -hA gi Λ | 3 sSoSO) 00), 3H 3> b 3 - ^ - 10 η 'η § 2 A _Q --1. 2 q 0OViOVil <ï-f-P3 03 ΛΟΟΟ ^ VSo.SCT'S 3Γ i · 0 «> AA AA AA A £ S.SAS A | 3¾ 3S bTv!

0 HO HO i>. O «b blioHHH 5 SA

> & .S ÉS 5.S ê§ Éo HH É >> £ .3 H & | I O

Ö-PS-Pë 0 ë P 0 -pH r ^ r ^ sPP -P r * s ö C? Ti <D (ü3 <Dc3? -LCd (DH <D> ï, ΰ ö <D 2 SS ^ Soo oS 'MHH3HOHS-5 3 ft -PO 3 PI 2 In £ 2? 2 ^ |

• S & £ £ & 3 £ Ω 7 S 2 i -S S -Λ 3 S I £ 3 f HHH

'ÖoBS.SASSICVI b S * SS /? Yy o o I H S 0 s33

.s ra “£ ° $ Vs“ hs. §3 “v” § l £ 5 "s III

£ 5 2 ïï 2 Ag ATS A & i! 5 & ΑΎ3 A§ & 3 Si'TB -fS

1 ± è .4A ^ A a £ 2 S J A ”iB .42 S ü .42 S ώ S S

7906019 - 16 'v- v Η £

YOU

j> 3 -4 -4 -4 -4 -4 -4 -4 -4 -4 -4 * -4 Ο

Η Ο CQ

3 ο or, 4- -4 · -4 4 4 -44 4 4 0 m 3 «ι-ί) • Η Ö cd Ρ II II a

tad I Η · -> I a I 3 I

a '1 · η ο ho ρ—' θ'— • HI ίο Η I ÖÖ-HS30 J0 Ή Α μ Ö> 5 I Α 3 · Η 3 · Η «Ö Η Ö pat 3 · η ρ Α ι 3 ι pg «A η · η · η

• Η S'— S a | ρ 3 3 ^ 5η 3 ρ 3 · Η S Ρ S

, |> «Ο ν 3>, α> 30« ο «η 5η η öcd ρ cd. Ρ Η Ö Η Η Μ I ίπ Ν · a Ha ρ> »3 £>’ 3η ο η • Η · Η · Η · Η ^> 5 Ο. Μ 0 Η · Η · Η · Η a 3 Ο 3 Ρ rj S3 3 ».

a a i ga ρ o ρ · η § ga o o a o a ö i ö 33 30 p o ra g 3 33 pp op 30 on o

0 ρ H pp OHO) 3 Η ρ Η H 5h 3¾ OP 1 P

Tj a Sn 5h 5h i Ρ IP!> »5h Sn ft 3 H 3 a H a 3 3 3 3 IO ι — ι aa 3 a ΙΟ a OO 3 H 3 CQ OO OO CQtI rl 3 0 OO 4 Η IHOO b ü aip in ia> sop ip ι b 4 b hh ρ h 0 ^ a ^ ί> ί paia -— a ft ia pb -Pb

60 H 3 HP H - 0 3 H 3 HO O O P O P

h> »o> j-p> i ι ft h o l> sO s a na ip ^ 53

Pc ΡΗ Ρ 0 pcni i ^ H PH P ft fe> Pn 000 MP

> p>, pa ρ1 —'— p b p b p o ρ o ι a o 1

0ft 0a 010 P ft 01¾ 0 H PH Ha. p P

a i> soa '> joa s> j a a 00a s 0 a i> s 0 a 0 ο .a i >> 0 a p a a 0 wa3 MO0 μ3 · η ^ a 0 m a 0!? ϊ> »0 <u P q 0 000/0 M 0 ftp OHP 03a M ft P Oftp OOP MOPPHP θΡΡΗ a pom ppm pn 3 00m a 0 m pw .m 0 m 0 pmh ^ ra 0 .¾ ΡΗ0 PO0 PHH ΡΗ0 ' ÖH0 ΡΙ0 ΡΙ0 a O 0 fl I 0 H.

(3 0 α ι 0 · η 1 0 · η> 5 po 1> 5 ο ι 0 on 1 p on 1 a · η 1 1 on 1 a as> sr-i sa 1 — is 0 aw> 51—1 a hn s1—11—1 Ö1 — ί — 1 3 ar1 cmi — ti 3

• Η \ Ο Η I Ρ Η I 3 Ο I Ο Η I ϋ H 1 I d I J H 3 Ρ H *> I Η P

a - 'ι a -' 1 a - · aa - * 1 a —- 1 a · - 3 a - * aa 0 1 a - a a- p 0 1000 1000 133 1000 1000 130 1 a, 0 1 - m 0 i 3 <u - a> a 1 — ip a> —1 ρ a ο o a1 —'ft s '-' ft sn ft 3 «ft a1 —ft a ^ ft 0 7906019 17

Example YII

Ιο. In a greenhouse, the plants listed in the table below were treated after emergence with the agents indicated in that table in an amount of 3 kg of active compound / ha.

The agents were sprayed evenly over the plants for this purpose. The treatment result was achieved by evaluation »where: 0 -" totally destroyed "and TO =" unaffected "mean» Here, three weeks after the treatment, the agents according to the invention were found to have a high selectivity with excellent action against weeds. The comparators did not show this selectivity.

7906019

V

- 18 * ds Boxss ^ ag; o o o o o o • ds' BTjrsq.ss o o o o o o o • ds ïïtn.tnrB'i o o o o o o o • ds' BSTHOdj o o o o o o o 'BTfscBty; ο ο ο ο σ o o • ds nmuBTog ο ο ο ο ο ο o • ds: 'Bx ^ ndostLC-o ο ο ο ο ο ο o

isCtw o o o o ir \ CO

~ · · * - * r · »8 Cog o o o o o · - T-

U30Q.8] Y O O O O O O O

trsxsddspj'BV o o o o o itn co usq.sxqj: s2rTng ι o o o o o o tc g

• H

rö I

ö H

• Η · Η I ON Ê4 I fi | H CO O 0

-p I HI cö H! j >> CM -P * P

• Η 1 Η £> ιΗ, Ο Η H · W CQ

3 Η Λ> 5 U \ Hfl · Η O be VO 0.10 >> d +5 G cd- 'rj Q a H c1, ¾ J + 1, 0 °. 1

<D, G O (DO CO £ · Η g (d> VO Pill — I 1 - '(- I

-G -P * H a -Η rj G -P ft G3> ^ ^ Η I H

(U ft I ft >> · Η 0) 0 Snr-f ö. ·

m SO COO Λ S IP a5> 5 <d P P G G G

g ι pu ι uu +> 3 3 ft p ο λ p η λ g, <u G <u φ onpidi ^ ft® jin iv — oji.paj oodftNft bC I —'- PH - -P SI> j -— 1 -P '-' Sti ^ -ra Η I ca> s I 03 |. G H CO 03 H g 03 G · Η (D ^ G ^

o rl ΓΟ (D i! 00 'β C00 S1—1 (D> * · Η ID · Η O- S Ο · Η O

b. ^ ¾1—1 I -P 1—1 I I -Η N ι ι λ G I ö Ο -H G Ö G

G I '- I (Dll - ι H ft 0¾1 - 1 +) 1 .1 - ι 03 p g · Η Ο · Η G -PPHSP. Hi >> 0.p (l) GH- <U <NH Ü1 + «S ί | δ <D 3!> ϊ '5? 3> 0 Λ p tD fit G> t P "> 5 G U £> 3 P CÖ

b £ GGGOGG -Pft + 3GNGOOJG-HOPH ajH

G g «(D + 3N <D <D '—- mg 000 ^ - 0) ^ g> 5 h> 5 • H cd H CM - (Jr— | CM SI <U ¢ 00 (+ - (HI ( + -4

rtf |> 5 -Η I Ο -Η I 2 co I -Η I +3 CO ι -Η ϋ Η 0 ί> 9 O

GOG 1—1 2 C · - σί (—'I — IO g O'— H CQ ... >> · Η -P · Η • Η I δ Ο IGOSI Η I δ Ο II 0 <D * H -P ft G ft fQ CM +3 G 0J +3 G> i P> sa +3 G CM PGM tso G Ο Λ Ο T !. p · η -> p · η o GG · - 'p · ρ -' 2 ' d PH wa ^ a (D lcdSigglG <DlSai GS <D (D | ftWft> a_aasog_BNCHSoSB «g> W G'wH'- '7906019

Claims (40)

19 '• 5- s> 1. Carbamic acid phenyl esters of the general formula 1, wherein: R 1 C 1 -C 8 -alkoxy-C 1 -C 6 alkyl, di-C 1 -C 1 -alkoxy-C 1 -C 2 -alkyl, cyano-C 1 -Cg- alkyl, halo-C 1-6 -alkyl, phenyl-C 1-6 -5 -alkyl, 1,3-dioxolan-2-yl-methyl, 2-methyl-1, S-dioxolane - ^ - yl-metliyl, 2,2-dimethyl-1,3-dioxolan-4-yl-methyl or aminocarbonylmethyl; Eg phenyl, phenyl singly or multiply substituted by halogen and / or methyl and / or methozy; and R 1, C 1 -C 8 alkyl, C 1 -C 8 alkenyl, cyelopropyl or trichloromethyl or methyl or ethyl; R1-cyano-b-phenyl or 1-cyano-2-phenylethyl; and R 4 represent ethyl. 2. N- (2,2-Diethoxyethyl) -earbanilic acid- [3- (2,2-dimethylvalerylamino) -phenyl] -ester. 3. ΕΓ- (2-Cyanoethyl) -3-methyl-arbanilic acid- [3- (tr-1-chloromethylcarbonylamino) -phenyl] -ester. {N-Cyanomethylcarb anilic acid [3- (tert-butylcarbonyl-20 amino) -phenyl] ester. 5. ΪΓ- (2-Cyanoethyl) -carbanilic acid [3- (cyclopropyl-carbonylamino) -phenyl] ester. 6. N- (2S 2-Dimethoxyethyl) -carbilic acid- [3- (propionylamino) -phenyl] ester. N-Cyaarmethyl carb anilic acid [3- (propionylamino) phenyl] ester. 8. F- (2-Cyanoethyl) -3-methylcarbilic acid [3- (propionylamino) -phenyl] ester. 9. T- (2-Methoxyethyl) -carbilic anilic acid - (3- (pr opi onylamino-30 no) -phenyl] ester 10. T - (2-Cyanoethyl) - - methylcarbanilic acid [3- (propio -nylamino) -phenyl] ester. 11. N- (2-Cyanoethyl) -2-methylcarbanilic acid [3- (propio-7906019. V-, -2O; 2Q. "<-Ylamino) -phenyl] -ester. 12. N- (2-Methoxyethyl) -3-methylcarbanic acid [3- (propionylamino) -phenyl] ester. 13. H- (2,2-Dimethoxyethyl) -it-methyl-arbanilic acid [3- (pro-5-pionylamino) -phenyl] -ester. 1k. N- (2,2-Dimethoxyetbyl) -3-methylcarbanilic acid [3- (propionyl amino) -phenyl] ester. 15. N- (2-Bromoethyl) -carbanilic acid [3- (propionylamino) phenyl] ester. 16. N- (2-Ethoxyethyl) -carbanilic acid [3- (propionyl amino) phenyl] ester. N- (2-Cyanoethyl) -carb anilic acid [3- (propionylamino) -phenyl] -ester. 18. "H- (2,2-Dimethoxyethyl-2-methylcarbanilic acid- [3- (pro- 15'-pionylamino) -phenyl] -ester. 19,1T-Cyanomethyl-3-methylcarbanilic acid- [3- (propionyl- amino) -phenyl] ester. 20. H- (1-Cyano-2-phenyl-ethyl) -N-methyl-carbamic acid- [3- (propionylamino) -phenyl] -ester. 21. IT- (α-Cyano-benzyl) -H-ethyl-carbamic acid [3- (propi onylamino) -phenyl] ester. " 22. H- (1,3-Dioxolan-2-yl-methyl) -carbanilic acid [3- (propionylamino) -phenyl] ester. 23. 3-Methoxy-I- (2-methoxyethyl) -carb anilic acid [3- (propy-pionylamino) -phenyl] -ester. 2k. N- (U-Methyl-1,3-dioxolan-2-yl-methyl) -carbanilic acid [3- (propionylamino) -phenyl] ester. 25. U-Cyanomethylcarbanilnur- [3- (2,2-dimethylvalerylamino) -phenyl] ester. 26. flf- (2-Cyanoethyl) -carb anilic acid [3- (2,2-dimethylYalearylamino) -phenyl] ester. 27. II- (2-Cyanoethyl) -carb anilic acid [3- (2-methylpropionylamino) -phenyl] ester. 28. N- (2-Chloroethyl) -carbanilic acid- [3- (2,2-dimethyl-35-valerylamino) -phenyl] -ester. 7906019 21. -Jr 29. IT- (2-Chloroethyl) -carbanilic acid- [3- (propionylamino) -phenyl] -ester- 30. IT- (2-Phenylethyl) -carbanilic acid [3- (propionylamino) phenyl] ester. 31. IT- (2-Cyanoethyl) -carbanilic acid [3- (crotonoylamino) phenyl ester. 32. IT- (2-Chloroethyl) -caranilic acid- [3- (crotonoylamino) -phenyl ester. 33. IT- (2,2-Dimethoxyethyl) -carbanilic acid [3- (2,2-dime-10-thylvalerylamino) -phenyl] -ester. 34. IT- (Aminocarbonylmethyl) -earbanilnur- [3- (cyclopropylcarbonylamino) -phenyl] ester. 35. IT— (2-Aminoearbonylethyl) -earbanilznur- [3- (cyclo-propylcarbonylamino) -phenyl ester. 36. N- (2-Cyanoethyl) -3-methylcarbanilaziar- [3- (cyclopropylcarbonylamino) -phenyl] ester. 37. N- (2-Cyanoethyl) -3-methylcarb anilic acid [3- (tert-butylarbonylamino) -phenyl ester. 38. IT- (2-Cyanoethyl) -earbanil zur- [3- (tert-butylcar-20-bonylamino) -phenyl ester. 39. IT-Cyanomethylcarbanilic acid [3- (trichloromethylcarbonylamino) phenyl] ester. 40. IT- (2-Cyanoethyl) -carbanilic acid [3- (trichloromethyl-carbonylamino) -phenyl] ester. 41. IT- (2,2-Dimethyl-1,3-dioxolan-4-yl-methyl) -carbanilic acid [3- (2,2- <imethylvalerylamino) -phenyl] ester. 42. IT- (2-Methoxyethyl) -carb anilic acid [3- (tert-butylcarb onylamino) -phenyl] ester. 43. IT- (2-Methoxyethyl) -3-methoxycarbanilic acid [3- (tert-30-butylarbonylamino) -phenyl] -ester. 44. H- (2-Methoxyethyl) -carbanilic acid [3- (cyclopropylcarb onylamino) -phenyl ester. 45. IT- (2-Methoxyoxy) -carbanilic acid [3- (trichloromethylcarbonylamino) phenyl] ester. 35 IT- (2-Methoxyethyl) -3-m.ethoxycarbanilic acid- [3- (tr i-7906019 * 1 22 "7-" V chloromethylcarbonylamino) -phenyl] ester. 1 + 7 · IT- ( 2-Ethoxyethyl) -carbanilic acid- [3- (cyclopropyl-carbonylamino) -phenyl] -ester 1 + 8, iT- (2-Hydroxyethyl) -carbanilic acid- [3-cyclopropyl-5-carbonylamino) -phenyl] -ester 1 +9, IT- (2-Methoxyethyl) -4-fluorobarbanilic acid (3- (cyclopropylcarbonylamino) -phenyl) ester. 50. IT - (2-Ethoxyethyl) -1 + - fluorocarbanilic acid (3-cyclopropylcarbonylamino) phenyl) ester. 51- II-Cyanomethyl-3-chlorocarbanililin [3- (trichloromethylcarbonylamino) -phenyl] ester. 52. E- (2,2-Dimethoxyethyl) -3-methylcarbanilic acid [3- (tert-butylcarb onylamino) phenyl] ester. 53. A process for preparing carbanil acid esters, characterized in that carbanil acid [3- (alkylcarbamoylanri.no) -phenyl] esters according to any one of claims 1 to 52 are prepared using a method known for analogous compounds . 5I +. Process for the preparation of carbanilic acid esters, characterized in that carbanilic acid [3- (alkylcarbamoylamino) -phenyl] -20 esters according to any one of claims 1 to 52 are prepared by: compounds of the general formula 2, in the presence of organic bases or in the form of alkali salt and, either to be reacted with compounds of the general formula III or with phosgene with the addition of inorganic or organic bases of addition to the corresponding chloroformic acid esters of the general formula 1+ and subsequently reacting them with compounds of the general formula V in the presence of bases and isolating the obtained products in a manner known per se, wherein in the said formulas, R 1 and R 2 have the meanings mentioned above, 55. A method for preparing a herbicide, characterized in that one or more of the compounds mentioned in claims 1 to 52 are brought into a form of herbicide suitable application. 7906019 23. 56. Herbicide formed, obtained by the method according to claim 55 A herbicide, characterized in that it contains a carbamic acid phenyl ester prepared by the method of claim 5¼. ƒ 7906019 · & - · - ·> - V t I ’_i R, / 0. CO - N! Λ - NH - CO - R3 OH _L Π (I J- NH - CO - J_ - co - ci R2 0. CO - Cl · U - m - “- E3. ___ A NH R2 ^ SCHERI1G AKTIENGESELLSCHAFT 7906019