DE3410317A1 - NEW ANILINE COMPOUNDS AND THEIR USE - Google Patents

Description

SANDOZ-PATENT-GMBH ■ Case 133-0583

7850 Loerrach

New aniline compounds and their application

The invention relates to new substituted phenoxyanilines and Pyridyloxyaniline, intermediates therefor and the application these compounds in weed control.

The new compounds according to the invention have the following formula I

^Y t

where M is CH or N,
t stands for 0, 1 or 2,
X stands for O or S,
Y and Z, independently of one another, for H, C -, _ g-alkyl,

C, _galkoxy, C, ghaloalkyl, C-, ghaloalkoxy, halogen, CN and NO ₂ stand,

R is C _1-8 alkyl, C ₂ _ _g alkenyl, _C2-8 alkynyl, C ^ gHaloalkyl, C ₂ _gHaloalkenyl., CogHaloalkynyl, C _2-8 (Al koxyal alkyl). C ₂ _ ₈ (alkylthioalkyl), C ₃ _ ₈ cycloalkyl, phenyl-C ^ galkyl, or represents one of the meanings given in the following for R ^1;

\ j "-r ι w vy ι ι

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R ^{1 represents} H, or a group A;

A for CN-C ₁ "alkyl, (CHR ¹ J _n -COOR ² , (CHR ³ ) -COR ⁴ , (CHR ³ ) -SO ₉ -R ¹ ,

ς> ~ ^ö cg ⁿ inn ¹¹ ι? ^{n ά}

(CHR ^s ) _n , 0-CO-R, (CHR ^) _n , -CO-O-CR ¹ V-COOR ', {CH ₂ ) _n , -W-

(CH ₂ ) _n "- W'-R ¹³ or C0-CHR ¹⁴ -0R ¹⁵ ; R "represents NO ₂ , NH ₂ , CN or Cl,

R ^{1 represents} H, C _1-8 alkyl, C _1-8 alkoxy or C _1-3 alkylthio,

R and R Hj a metal cation, C ₁ ^ alkyl, C _2-3 alkenyl, C _2-8 kynyl Al, C ^ _{1 Q} (Al kyl thi oal kyl), C ₂ _ _1Q (alkoxyalkyl), C ₁ _gHydroxyalkyl, C _2-1Q (alkylsulfinylalkyl), C _2-1 qAIkylsulfonylalkyl, substituted or unsubstituted phenyl, C _3- gCycloalkyl, C, gHaloalkyl, C _3-3 (alkoxyalkoxyalkyl), C "_gAlkylamino, di (C, Gal alkyl) ami no, C _3-3 CyCl oal kyl-C-. , alkyl, a saturated 3-8-membered heterocyclic group with one or 2 heteroatoms selected from 0 and N, substituted or unsubstituted benzyl or a group N = C (R) ₂ ", R ³ and R ^{14 represent} H or C _1-3 alkyl;

4th
R for C-, JUkyl, C _2-3 Al kenyl, C _1-3 Al kyl thi 0, C _1-3 Al kyl ami no, di (CJ _-8 Al kyl) ami no, C ₃ «Cycloalkyl, C, Jhaloalkyl, substituted or unsubstituted phenyl, substituted or unsubstituted benzyl, substituted or unsubstituted anilino or

the group CHR ⁵ ^ COOR ¹⁶ stand,. ·

R and R independently represent H or C _1-3 alkyl;

R ^{6 represents} C _1-8 alkyl, C _2-8 (alkoxyalkyl), C _3-3 CyClOaIkyl., C _1-8 haloalkyl, or substituted or unsubstituted phenyl; .or

R and R together _{stand for C 2-.} Alkylene or C _2-4 alkenylene, R ⁸ and R ¹³ stand for C _1-3 alkyl,

R ₅ R and R independently of one another for H, C, "alkyl, C _1-3 AlkOXy or C _1-3 alkylthio,

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R stands for substituted or unsubstituted phenyl or substituted or unsubstituted phenoxyphenyl,

η stands for 0, 1 or 2,

n 'and n ¹¹ , independently of one another, stand for 1 or 2 and W and W, independently of one another, stand for 0 or S.

The terms "substituted phenyl", "substituted benzyl" and "substituted anilino" stand for a phenyl, benzyl or anilino group which is mono-, di- or tri-substituted in the phenyl ring by substituents of the series C, _g alkyl, C, gHaloalkyl, C, "alkoxy, C2_gAlkenyl, C2_gHaloalkenyl, C ₂ oAlkenyloxy, halogen, NO _2, CN or C, gAlkylthio. The term “substituted phenoxyphenyl” stands for a phenoxyphenyl group which is mono-, di- or trisubstituted in the phenoxy radical by substituents of the series C, g-alkyl,. C- | _ghaloalkyl, C-igalkoxy, C, ghaloalkoxy, C ₂ _gATkenyl, C ₂ _ghaloalkenyl, C _2-8 alkenyloxy, halogen, NO ₂ , CN or C _1-3 alkylthio.

The term C ₂ _ ₈ alkenyl refers to an unsaturated C _2-8 hydrocarbon group which has 1 or 2 double bonds.

The term Co galkynyl refers to an unsaturated C ₂ ″ g hydrocarbon group which has 1 or 2 triple bonds.

The terms C, ghaloalkyl, C-, ghaloalkoxy, C ₂ _gHa1oalkenyl and C ₂ _ghaloalkynyl relate to Cj_gAlkyl, Cj_galkoxy-C ₂ _gAlkynyl and C ₂ _galkynyl groups which are substituted by 1 to 3 halogen atoms.

2 12 Examples of suitable metal cathion meanings of R and R include the cathiones of the alkali and alkaline earth metals, such as Li, Na, K, Ca, Ba, Sr and Mg.

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R is preferably C. alkyl, more preferably C, »alkyl and especially

1-8 ~

special CH ₃ .

Aliphatic hydrocarbon substituents of the compounds of the formula I preferably have no more than 4 carbon atoms; Alkyl substituents or alkyl parts of substituents of the compounds of the formula I have more preferably 1 or 2, in particular 1, carbon atom; suitable examples of alkenyl and alkynyl substituents of the compounds of the formula I include CH ₂ —CH = CH ₂ and CH ₂ —CSCH.

2 A suitable example of a heterocyclic group R or R is 2-tetrahydrofuryl.

•? · A suitable example of a C ^ cycl oal kyl -C-, ^ aI kyl group R or R is cyclopropyl-ethyl.

The term halogen refers to F, Cl, Br and I, in particular F and Cl.

The invention also relates to methods of making compounds of formula I by

a) the activated NO ^ group in the 2-position of a 4-substituted-1,2-diN02-benzene compound of formula II

II

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wherein X, Y, Ζ, · M and t have the above meaning, by a Alkoxyamino group of formula III

NH-OR · III

where R has the above meaning,

substituted, and optionally in a suitable order so introduced alkoxyamino group by a group A, which has the above meaning, N-substituted and / or those in the ortho position of introduced alkoxyamino permanent NO ^ group to a NHp group hydrogenated, and / or the latter NHp group by Cl or replaces a CN group and / or a susceptible carboxyl ester group hydrolyzed to the free carboxyl group or to a salt converts from it, or

b) to compounds of the formula Ia

.NR ¹ -OR

Yes

in which X, Y, Z, M, t, R and R 'have the above meaning, obtained by adding a compound of the formula Ib,

ft NH-OR

Ib

- AA-

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wherein X, Y, Z, M, t and R have the above meaning, through a group A, which has the above meaning, N-substituted.

A suitable reaction scheme is as follows:

Formula II

Id

NR'-0R

Yes

Ic

Depending on the meaning of the substituents, there may be a different one Order more displayed.

The above preparation of the compounds of the formula Ib is expediently carried out using the alkoxyamino compound (H ₂ NOR) in salt form, for example as the hydrochloride, and in the presence of a base such as K ₂ CO ₃ . A suitable reaction medium is, for example, an organic solvent which is inert under the reaction conditions, such as CH ₂ Cl ₂ , tetrahydrofuran (THF) or N, N-dimethylformamide (DMF). The reaction can take place at room temperature.

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The N-substitution of a compound of the formula Ib can be carried out analogously to known N-alkylation processes can be carried out. Suitable Alkylating agents are, for example, compounds of the formula IV

A-HaI IV

where A has the above meaning

and Hal is halogen, e.g., Cl or Br, or reactive ^ capable functional derivatives thereof such as acrylates, anhydrides, etc.,

If a compound of the formula IV is used as the alkylating agent, it is expedient to work in an organic solvent which is inert under the reaction conditions, such as acetone, CHpCl ₂ , 2-butanone, benzene or DMF. The presence of a base such as triethylamine, K ₂ COo, pyridine or NaH can be advantageous. A suitable reaction temperature is room temperature or a higher temperature. The compound of the formula Ib can also be converted as the N-metal salt (see, for example, Example 7).

The hydrogenation of the above compounds of the formula Ia to compounds of the formula Ic (see reaction scheme) can be carried out by selective .Hydration of the NO ₂ groups to the NH ₂ group by known methods, for example with. With the help of NaBH or analogous hydrogenating agents.

The conversion of compounds of the formula Ic to compounds of the formula Id can be carried out according to _{methods known for the substitution of an aromatic NH 2} group by Cl or a CN group. An example of a suitable implementation is the diazotization of the NHp group by known methods, for example using HCl and HNO ₂ , as described, inter alia, in Org.Synth.Coil. Vol. 1: 514 (1932), and subsequent reaction of the diazo compound with copper (I) cyanide or copper (I) chloride according to Sandmeyer.

OM- I UJ I /

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The hydrolysis of a precipitated carboxyl ester group of the compounds of the formula I to give the free carboxyl group can be carried out by methods known per se, for example with the aid of a base such as NaOH in a suitable solvent such as CH ₃ OH which is inert under the reaction conditions. Such free acids can be isolated as such or as salts (alkali or alkaline earth metal salt), to which the free acid can be converted by means of a strong base (such as a metal hydride, for example).

The compounds of the formula I can be isolated and purified from the reaction mixture in which they are obtained by known methods will.

If the preparation of the starting compounds is not described, these are known or analogous to known or herein described method can be produced.

The compounds of formula I are useful for combating Weeds using pre- and / or post-em treatments. The compounds can be used as dust formulations, granules, Solutions, emulsions, water-dispersible powders, suspension concentrates and suspensions can be applied. The application a compound according to the invention is carried out by known methods to the weeds or their place of growth using a herbicidally effective amount of the compound, generally between about 100 g and 10 kg / ha. .

The compounds according to the invention have a favorable herbicidal properties Broad spectrum action on both broad-leaved as well as grass-like weeds, the optimal application of a compound according to the invention can easily be carried out by the person skilled in the art by means of

133-0583

Routine tests, such as greenhouse or small plot tests, be determined '. ·

In general, however, satisfactory results are obtained when the compound of the invention in an amount of 0.1 to 5 kg / ha, preferably 0.2 to 4 kg / ha, more preferably from 0.5 to 3 kg / ha is applied, the treatment if desired can be repeated.

The compounds according to the invention are relatively less toxic to useful plants than to weeds. A selective one herbicidal effect is. in grains like wheat, and barley Rice, in cotton, in soybeans and especially in corn have been observed. The use of these compounds as selective herbicides is accordingly displayed.

As used herein, herbicide refers to an active ingredient that affects plant growth, either due to its phytotoxicity or its regulating plant growth Properties for the purpose of retarding the growth of the plant or for the purpose of sufficient damage to the plant, which is sufficient, to kill them.

'20 Preferred compounds have one or more of the following Characteristics;

- M is N,

- t is 1,

- Y is in the 0 position and Z is in the p position,

- Y is. H or o-Cl, preferably o-Cl,

• - Z is p-Cl or P-CF ₃ , preferably P-CF ₃ J

- R ¹ is (CHR ¹ J _n -COOR ² , CO-CH ₂ -COOC ₁ _ ₄ alkyl, CO-C ^ alkyl,

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- η is 0 or 1, preferably 1,
. - R ¹ is H or CH ₃ ,

- R ² IStC _1-4 AIkYl, C ₁ _ ₂ alkyl-O (CH ₂ ) _{1 v} CH ₃ -S

CH ₃ -S0- (CH ₂ ) ₂ , CH ₃ SO ₂ CH ₂ CH ₂ , benzyl, cyclopropyl-CH ₂ CH ₂ , Cl-CH ₂ CH ₂ , CH ₂ -CH = CH ₂ , CH ₂ -C = CH or 2-tetrahydrofuryl

and is preferably CH ₃ ,

- X is 0,

- R is CH ₃ ,

- R ¹ is CH ₂ -COOCH ₃ ,
. - R "is NO ₂

The compounds of the formula I are expediently used in the form of herbicidal preparations together with for agriculture acceptable diluents. Such preparations are also the subject of the invention. In addition to a compound of the formula I as an active ingredient, they can contain other active ingredients such as herbicides. They can be in solid or liquid form, e.g. as water-dispersible powders or suspension concentrates, as Emulsion concentrate, as a dust formulation, as granules, as Retard form. Such preparations can by known methods, e.g. by mixing the active ingredient with a thinner and optionally additional auxiliaries, such as surface-active agents Substances, can be obtained.

With diluents are liquid or solid, in agriculture Acceptable materials meant that are suitable for the Bringing the active substance into a form that is easier or better to apply, or to a useful or desired degree of effectiveness to dilute. Examples of such diluents are talc, kaolin, Diatomaceous earth, xylene and water.

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In particular, formulations which are used in the form of a spray be, .like. e.g. concentrates dispersible in water or wettable powders, may contain surface-active compounds such as wetting or dispersing agents, e.g. the condensation product of formaldehyde with naphthalene sulfonate Alkyl aryl sulfonate, a lignin sulfonate, a fatty alkyl sulfate ethoxylated alkylphenol or an ethoxylated fatty alcohol.

In general the formulations contain from 0.01 to 90% % By weight active substance, from 0 to 20% one for the farmers' Shank of acceptable surfactant and from Io to 99.99 ^. Thinner.

Concentrated forms of formulations, e.g. emulsion concentrates, generally contain between about 2 and 90, mostly • between about 5 and 70% by weight of active ingredient.

■ Application forms of such compositions generally contain between 0.0005 and 10% by weight of a compound according to the invention as an active ingredient. Typical spray suspensions can be used for Example contain 0.0005 to 0.05, advantageously 0.001 to 0.02% by weight, of active ingredient.

· The following examples illustrate the invention. Temperatures are given in degrees Celsius, RT stands for room temperature, THF for tetrahydrofuran and TLC for thin-layer chromatography. "Parts" are parts by weight.

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Formulation Example 1: Water Dispersible Powder

25 parts of a compound according to the invention are combined with 3 parts Na lauryl sulphate, 5 parts Na lignosulphonate, 22 parts synthetic, fine silica and 45 finely divided kaolinite Ground until the mean particle size is below

5 microns is. The powder obtained in this way is with before use 'Diluted water.

Formulation Example 2: Emulsion Concentrate

25 parts of a compound according to the invention are mixed with 10 parts of an emulsifier (e.g. a mixture of an ethoxylated alkylphenol with calcium dodecylbenzenesulfonate) and 65 parts of xylene mixed. This concentrate is diluted with water to the desired concentration before use.

Example 1: N-Methoxy-2-nitro-5- (2-chloro-4-trifluoromethylphenoxy ) aniline

A mixture of 4- (2-chloro-4-trifluoromethylphenoxy) - !, 2-dinitrobenzene (1000 mg), methoxyamine hydrochloride (362 mg), K ₂ CO ₃ (762 mg) and THF (15 ml) is used for 4 days stirred at RT. The reaction mixture is then filtered and the filtrate is evaporated to dryness. The residue is taken up in ether, the solution is washed, dried and evaporated to dryness, and after purification by column chromatography gives the title compound, mp 105 °.

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Example 2;

The procedure is analogous to the process according to Example T and, by reacting a 4- (substituted phenoxy.) -! , 2-dinitrobenzene or 4- (substituted 2-pyridyloxy) -l, 2-dinitrobenzene compound with an alkoxyamine hydrochloride the corresponding compound of Formula I (table A)

Table A (X = O, R = CH ₃ , R ¹ = H and R "= NO ₂ )

M. Z Yt • R 2.1 CH 4-CF ₃ H CH ₃ 2.2 CH 4-CF ₃ 2-F CH ₃ 2.3 CH- 4-Cl 2-NO ₂ CH ₃ 2.4 CH 2-Cl 6-Cl CH ₃ ' 2.5 CH 4-CF ₃ 2rCl-6-F CH ₃ 2.6 N 4-CF ₃ 2-Cl . CH ₃ 2.7 CH 4-Cl 2-Cl ' ^CH 3 2.8 N 3-Cl 5-Cl: .CH ₃ 2.9 CH 4-CF ₃ 2-Cl ^C 2 ^H 5

⁽¹⁾ NMfl (CDCl ₃ ) r 6.25 (s, 3H, NOCH ₃ ), C3.44 (dd, IH, 8 Hz),

2.90 (d, IH, 2Hz), 1.87 (d, IH, 8Hz) phenyl H], [2.17 (d, IH, 2Hz), 1.77 (d; 1H, 2Hz) pyridyl H].

ο "-r ι \ j ^ j ι /

133-0583 ■

Example 3: N-Methoxy-N-methoxycarbonyl-2-nitro-5- (2-chloro -4-trifluoromethylphenoxy) -ani1i

To a solution of N-methoxy-2-nitro-5- (2-chloro-4-trifluoromethylphenoxy) aniline (660 mg) in CH ₂ Cl ₂ (10 ml) are added triethylamine (0.5 ml) and at 0 ° Cl-COOCH ₃ (0.3 ml) was added. The reaction mixture is stirred for 16 hours at RT, poured into water and extracted with ether. The extracts are combined, washed, dried and evaporated. The residue is prepared by means of prep. TLC purified and gives the Ti te! Compound.

NMR (CDCl ₃ ) А6.24 (s, 3H, 0-CH ₃ ) and 6.19 (s, 3H, C (O) OCH ₃ ) -. IR (film) = 1730 cm " ¹ (C (O) OCH ₃ ).

Example 4 : N-Methoxy-N-methoxycarbonylmethyl-2-nitro-5- (2-chloro-4-trifluoromethylphenoxy) ani1i

■ A mixture of the aniline according to Example 1 (530 mg), BrCH ₂ COOCH ₃ (0.27 ml), K ₂ CO ₃ (303 mg) and acetone (10 ml) is refluxed for 4 hours. The reaction mixture is filtered and the filtrate concentrated. The title connection remains, which was created by prep. TLC is purified. MS m / e 434 (M ⁺ ).

Example 5: 2-Nitro-5- (2-chloro-4-trifluoromethylphenoxy) -N-methoxyacetanilide

Acetic anhydride (0.6 ml) is added to a solution of the aniline according to Example 1 (500 mg) in pyridine (5 ml). The mixture is stirred at RT overnight, then diluted with CH ₂ Cl ₂ and acidified. The phases are separated, the organic phase is washed, dried and evaporated. The crude product is prepared using prep. Purified TLC to give the title compound.

NMR (CDCl ₃ ) IT 7.74 (s, 3H, C (O) CH ₃ ), 6.24 (s, 3H, N-OCH ₃ ). IR (film) = 1690 cm " ¹ (C (O) CH ₃ ).

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- SO-

Example 6; N-methoxy-N-2-methoxycarbonylethyl-2-nitro-5- (3-

chloro-5-fluoromethyl-2-pyridyloxy) anTI Vn

Methyl acrylate (1.56 mmol) and a catalytic amount are added to a solution of N-methoxy - ^ - nitro-S-iß-chloro-S-trifluoromethyl-2-pyridyloxy) aniline (1.55 mmol) in CH _{3 OH (10 ml)} CH ₃ ONa given,. . The mixture is stirred for 1 hour at RT, then poured into water, acidified and extracted with ether. The combined extracts are washed, dried, evaporated to dryness and purified by means of prep. TLC, the title connection remains.

Example 7; N-methoxy-N-1-methoxycarbonyl-ethyl-2-nitro-5- (2-chloro-

4-trifluoromethylphenoxy) aniline

At 0 ° NaH (50 %, 72 mg ) given. The solution is stirred until the evolution of gas ceases (about 10 minutes) and methyl a-bromopropionate (276 mg) is added dropwise. The mixture is stirred for 6 hours at RT and then diluted with ether, poured into 10% aqueous HCl. And extracted with ether. The combined extracts are washed, dried and evaporated to dryness. An oily residue remains, which can be removed by means of prep . TLC to the pure Ti te! Connection is cleaned. ·

NMR (CDCl ₃ ) T8.45 (d, 3H, NCHCH ₃ , 6.67 (s, 3H COOCH ₃ ), 6.44 (s, 3H, NOCH ₃ ) x 5.90 (q, IH, NCHCH ₃ ).

■ -24-

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Example 8:

The procedure is analogous to one of Examples 3 or 4 and, by reacting a compound of the formula I in which R ^{1 is} H, is obtained with. compounds of the formula I following a halide (Table B).

Table B (X is 0 and R "is NO ₂ )

Verb. MZ Yt

1 CH 4-CF ₃ 2-Cl CH ₃ CH ₂ C ₂₃

2 CH 4-CF ₃ 2-Cl C ₂ H ₅ CH ₂ COOCH ₃

3 CH 4-CF ₃ 2-Cl CH ₃ CH ₂ COOt-C ₄ H ₉ (1)

4 CH- 4-CF ₃ 2-Cl CH ₃ CO-CH ₂ -CO-OC ₂ H ₅ (2)

5 N 5-CF ₃ 3-Cl CH ₃ CH ₂ COOCH ₃ MS m / e 435 (M ⁺ )

6 N 5-CF ₃ 3-Cl CH ₃ CH ₂ COOiC ₃ H ₇ MS m / e 463.8 (M ⁺ )

7 N '5-CF ₃ 3-Cl CH ₃ Ch ₂ COOCH ₂ CH ₂ OCH ₃ MS m / e 479.8 (M ⁺ )

8 N 5-CF ₃ 3-Cl CH ₃ CH ₂ -COO-CH ₂ Ch ₂ SCH ₃

9 N 5-CF ₃ 3-Cl CH ₃ CH ₂ COO-CH ₂ CH (CH ₃ ) ₂

10 N 5-CF ₃ 3-Cl CH ₃ 'CH ₂ COO- (Ch ₂ O ₂ OCH ₂ CH ₃

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verb

_Yt R -Bi

N N

5-CF 5-CF

3-Cl 3-Cl

.19 20 21 22 23 24 25 26 27 28

N N N N

CH

CH

CH

CH

CH

CH

CH

CH

5-CF

5-CF 5-CF 5-CF 5-CF ₃

5-CF ₃

5-CF ₃ 5-CF ₃ 4-CF ₃ 4-CF ₃ 4-CF ₃ 4-CF ₃ 4-GF ₃ 4-CF ₃ 4-CF ₃ 4-CF,

3-Cl

3-Cl 3-Cl 3-Cl 3-Cl

3-Cl3-Cl2-Cl2-Cl2-Cl2-Cl2-Cl2-Cl2-Cl2-Cl

CH ₃ CH ₃ CH ₃ CH ₃

3-Cl CH CH ₃ CH ₃ CH ₃ CH ₃ CH ₃ CH ₃ CH ₃ CH ₃ CH ₃ CH ₃

CH ₂ -COO-CH ₂ CH = CH ₂ CH ₂ -COO-CH ₂ CH ₂ Cl CH ₂ -COO-CH ₂ CaCH

CH (CH ₃ KOO-CH ₃ CH (CH ₃ J-COO-CH ₂ Ch ₂ OCH ₃ CH ₂ -COO-CH (CH ₃ ) ₂ ; MS m / e CH ₂ -COO-CH ₂ CH (CH ₃ ) ₂ ; MS m / e Ch ₂ -COO-CH ₂ CH ₂ OCH ₃ ; -

MS m / e

CH

CH CH

CH

CH

4-CF ₃ 2-Cl CH

4-CF 4-CF

4-Cl

4-Cl

5-Cl

5-Cl

5-CF ₃

5tCF ₃

2-Cl 2-Cl

2-Cl 2-Cl 3-Cl 3-Cl 3-Cl 3-Cl CH ₃ CH (CH ₃ J-COO-CH ₃ CH ₃ CH (CH ₃ ) -COO-CH ₂ CH (CH ₃ )

CH CH CH CH CH CH CH ₂ COOCH ₃ .

CH ₂ COOCH ₃

CH ₂ -COOCh ₂ CH ₂ IC ₃ H ₇ CH ₂ -C00CH ₂ CH ₂ tC ₄ H _g

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38 . N 5-CF ₃ 3-Cl CH ₃ CH ₂ -COO _n C ₄ H ₉ 39 N 5-CF ₃ 3-Cl CH ₃ CH (CH ₃ KOOCH ₃ 40 N 5-CF 3-Cl CH ₃ CH (CH ₃ ) -C00CH ₂ CH (CH ₃ ) ₂

'' analogous to example 4, in 2-butanone as solvent; NMR CCDCl ₃ ) TS.54 (s, 9H ₅ C (CH ₃ J ₃ ), 6.40 (s, 3H, N-OCH ₃ ), 6.10 (s, 2H, N-CH ₂ -); IR (film) = 1740 cm ' ¹ (C (O) O)

^ analogous to example 3; NMR (CDCl ₃ ) r 8.74 (s, 3H, OCH ₂ CH ₃ ), 6.37 (s, 2H, C (O) CH ₂ C (O)), 6.24 (s, 3H, N-OCH ₃ ), 5.84 (q, 2H, OCH ₂ CH ₃ ). IR (film) = 1695, 1740 cm " ¹ (C (O) CH ₂ (O) O).

Example 9: ■

N-Methoxy-N-methoxycarbonylmethyl-2-nitro-5- (2-chloro-4-trifluoromethylphenoxy) aniline is stirred for 30 minutes with 10 % NaOH (10 ml) in methanol (10 ml) at room temperature. The mixture is then poured into water and extracted repeatedly with ether. The extracts are combined. The free acid thus obtained is stirred with NaH (59 mg, 50 % oil) and anhydrous ether (4 ml) for one hour at room temperature. The solvent is removed. The solid residue is washed with pentane, dried under vacuum and gives the corresponding sodium chloride.

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Example 10:

The procedure is analogous to the process according to Example 9 and this is obtained the free acid of N-methoxy-N-methoxycarbonyl-methyl-2-nitro-5- (3-chloro-5-trifluoromethyi-2-pyridyloxy) anil in, which then with NaH is treated and the corresponding Na salt results'.

Example 11: N-Methoxy-N-methoxycarbonylmethyl-2-amino-5- (2-chloro-4-trifluoromethylphenoxy) ani1i

To a solution of N-methoxy-N-methoxycarbonylmethyl-2-nitro-5- (2-chloro-4-trifluoromethylphenoxy) aniTi η (868 mg) and anhydrous SnCl ₂ (2.25 g) in CH ₃ OK ¹ (140 ml) is given at 60 ° NaBH ₄ (30 mg) in CH ₃ OH over a period of 20 minutes. After the addition is complete, the reaction mixture is stirred for 30 minutes, then cooled to 5-10 °, water added and neutralized with dilute NaOH ^ The CHJDH is evaporated and the aqueous

] 5 solution extracted with CH ₂ CU. The extracts are combined, washed, dried and evaporated to dryness leaving the title compound.

Example 12 : ■

Analogously to the process according to Example 11, one obtains. N-methoxy-N-methoxycarbonylmethyl-2-amino-5- (3-chloro-5-trifluoromethyl-2- pyridyloxy) aniline.

Example 13:

The compounds according to Examples 11 and 12 are diazotized according to the Org.Synth.Coil. Vol. 1: 514 (1932). The diazonium salts thus obtained are treated with copper (I) cyanide (1.2 eq.) Treated in a benzene / water solution and give

UJ I /

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13.1 N-methoxy-N-methoxycarbony1 methyl-Z-cyano-6- (2-chloro-4-trifluoromethylphenoxy) ani1iη

13.2 N-methoxy-N-methoxycarbonylmethy1-2-cyano-5- (3-chloro-5-tri fluoromethyl-2-pyridyloxy) ani1i η

By reacting the diazonium salts with copper (I) chloride (1.2 eq.) you get

13.3 N-methoxy-N-methoxy-carbonyimethyl-2-chloro-5- (2-chloro-4-trifluoromethylphenoxy) anion

13.4 N-methoxy-N-methoxycarbonylmethyl-2-chloro-5- (3-chloro-5-tri fluoromethyl-2-pyridyloxy) ani1i η

A selection of the compounds according to the preceding examples is also characterized as follows:

Example NMR (CDCl ₃ ) f

6.40 (s, 3H, N-OCH ₃ ), 6.25 (s, 3H _1. OCH ₃ ), '5.97 (s, 2H,

3.33 (dd, IH, 8 Hz), 2.80 (d, IH, 8 Hz), 2.70 (d, IH, 2 Hz), 2.43 (dd, IH, 8 Hz), 2.30 (s, IH, 2 Hz), 2.03 (d, IH, 8 Hz) - aromatic protons.

8.5 6.37 (s, 3H, N-OCH ₃ ), 6.25 (s, 3H, COOCH ₃ ), 5.97 (s, 2H, NCH 3.04 (dd, IH, 8 Hz), 2.50 (d, IH, 2 Hz), 2.04 (d, 1H, 8 Hz) phenyl protons u

2.07 (d, 1H, 2 Hz), 1.80 (s, IH, -2 Hz) - PyHdyl protons.

8.6 8.72 (d, 6H, 6 Hz, CH (CH ₃ J ₂ ), 6.37 (s, 3H, N-OCH ₃ ),

(m, IH, OCT (CH ₃ J ₂ ), 3.04 (dd, IH, 8 Hz), 2.50 (d, IH, 2 Hz), 2.04 (d, IH, 8 Hz) - phenyl protons 2.07 (d, IH , 2 Hz), 1.80 (s, IH, 2 Hz) - pyridyl protons.

"■ **"" -SiQ '■ I ³³ - ⁰⁵⁸³

■ ο

8.7 6.64 (s, 3H, -OCH ₃ ), 6.44 (t, 2H, CO-CH ₂ -CH ₂ -O), 6.40 (s, 3H,

STILL ₃ ), 5.97 (s, 2H, NCH ₃ ), 5.70 (t, 2H, 0

CO-CH ₂ -CH ₂ O), 3.04 (dd, IH, 8 Hz), 2.50 (d, IH, 2 Hz), 2.04 (d, IH, 8 Hz) - phenylorotons; 2.07 (d, IH, 2 Hz), 1.80 (s,. IH, 2Hz) - pyridyl protons.

8.8 7.87 (s, 3H, SCH ₃ ), 7.39 (t, 2H, -CH ₃ S-), 6.40 (s, 3H, N-OCH ₃ ), 5.97 (s, 2H, NCH ₂ -), 5.70 (5 , 2H, OCH ₂ -), 3:04 (dd, IH, 8 Hz), 2.50 (d, IH, 2 Hz), 2.04 (d, IH, 8 Hz) - phenyl protons; 2.07 (d, IH, 2 Hz), 1.80 (bs, IH) - pyridyl protons -.-

8.9 9.08 (d, 6H, 6 Hz, CH (CH _-3 J ₂ ), 8.20 (m, IH, CH _- (CH ₃ ) ^, 6.40 (s,

'3H, N-OCH _7), 6:09 (d, 2H, 6 Hz, 0 ^j.

CO-CH _2), 5.97 (s, 2H, _N-CH2), 2.94 (dd, IH, 8 Hz), 2:54 (d, IH, 2 Hz)), 1.95 (d, IH, 8Hz) - phenyl protons; 1.98 (d, IH, 2 Hz), 1.70 (bs, IH) - pyridyl protons.

8.13 6..40 (s, 3H, N-OCH ₃ ), 5.90 (s, 2H, N-CH ₂ ), 4.84 (s, 2H, OCH ₂ ),

2.70 (s, 5H, -C ₆ H ₅ ), 3.04 (dd, IH, 8 Hz), 2.50 (d, IH, 2 Hz),

2.04 (d, 1H, 8 Hz) - phenyl protons; 2.07 (d, IH, 2 Hz), 1.80 (bs, IH) pyridyl protons,

8.15 6.37 (s, 3H, N-OCH ₃ ), 5.97 (s, 2H, NCH ₃ ), 4.75 (m, 2H, = CH ₂ ),

4.05 (m, IH, -CH =), 3.04 (dd, IH, 8 Hz), 2.50 (d, IH, 2 Hz), 2.04 (d, 1H, 8 Hz) - phenyl protons; 2.07 (d, IH, 2 Hz),

• 1.80 (bs, IH) - pyridyl protons.

8.19 8.47 (d, 3H, 7 Hz, NCH (C] I ₃ ) -), 6.37 (s, 3H, N-OCH ₃ ), 6J30 (s, 3H, COOCH ₃ ), 5.84 (q, IH, NCH (CH ₃ )), 3.30 (dd, IH, 8 Hz), 2.50 (d, IH, 2 Hz), 1.94 (d, IH, 8 Hz) - phenyl protons .; 1.90 (d, IH, 2 Hz), 1.70) bs, IH) - pyridyl protons.

Τ- 133-0583

8.21 8.75 (d, 6Η, 6 Hz), CH (CH ₃ J ₂ ), 6.40 (5, 3Η, N-OCH ₃ ), 6.04 (s, 2Η, N-CH ₂ ), 4.94 (m, CH- ( CH ₃ J ₂ ), 3.33 (dd, IH, 8 Hz), 2.80 (d, .lH, 8 Hz), 2.80 (d, IH, 8 Hz), 2.70 (d, IH, 2 Hz), 2.43 (dd , IH, 8 Hz), 2.30 (s, IH, 2 Hz), 2.03 (s, IH, 8 Hz) aromatic protons.

8.22 - 9.08 (d, 6H, 6 Hz, CH (CH_ ₃ ) ₂ ), 8.20 (m, IH, CHJCH ^), 6.40 (s,

3H, N-OCH ₃ ), 6.09 (d, 2H, 6 Hz, OCH ₂ -), 5.97 (s, 2H, NCH ₃ -),

3.33 (dd, IH, 8 Hz), 2.80 (d, IH, 8 Hz), 2.70 (d, IH, 2 Hz),

2.43 (dd, IH, 8 Hz), 2.30 (s, IH, 2 Hz), 2.03 (s, IH, 8 Hz) aromatic Protons.

8.23 6.64 (s, 3H, -OCH ₃ ), 6.40 (s, IH, N-OCH ₃ ), 6.44 (t, 2H, CO-CH ₂ CH ₂ O), 5.97 (s, 2H, NCH ₂ ), 5.70 (t, 2H),

CO-CH ₂ CH ₂ -O), 3.33 (dd, IH, 8 Hz), 2.80 (d, IH, 8 Hz),

2.70 (d, IH, 2 Hz), 2.43 (dd, IH, 8 Hz), 2.30 (s, IH, 2 Hz), 2.03 (s, IH, 8 Hz) - aromatic protons.

8.34 6.37 (s, 3H, N-OCH ₃ ), 6.25 (s, 3H, OCH ₃ ), 5.97 (s, 2H, NCH ₃ ), 3.08 (dd, IH, 8 Hz), 2.54 (d, IH, 2 Hz), 2.04 (d, 1H, 8 Hz) phenyl protons; 2.39 (d, IH, 2 Hz), 2.07 (bs, ίΗ) - pyridyl protons.

8.36 9.10 (d, 6H, 6 Hz, -CH (CH_ ₃ ) ₂ ), 8.44 (m, 3H, -CH ₂ CH (CH ₃ ),

6:37 (s, 3H, N-OCH ₃ ), 5.97 (s, 2H, NCH ₃ -), 5.84 (t, 2H, -OCH ₃ ), 3.02 (dd, IH, 8 Hz), 2.47 (d, IH, 2Hz), 1.97 (d, IH, 8 Hz) phenyl protons; 2.19 (d, IH, 2 Hz), 1.74 (bs, ΊΗ) -pyridyl -. protons. .

8.37 9.04 (s, 9H, C (CH ₃ J ₃ ), 8.44 (t, 2H, -CH ₂ ), 6.34 (s, 3H, N-OCH ₃ ), 5.94 (s, 2H, NCH ₂ -), 5.77 (t, 2H, OCH ₂ -), 3.02 (dd, IH, 8 Hz), 2.47 (d, IH, 2Hz), 1.97 (d, IH, 8 Hz) phenyl protons; .2.19 (d, IH, 2 Hz ), 1.70 (bs, IH) pyridyl protons.

133-0583

8.38 9.17 (t, 3Η, -CH ₃ ), 8.64 (m, 4Η, -CH ₂ CH ₂ ), .6.37 (s, 3H, N-OCH ₃ )

5.97 (s, 2H, NCH ₂ -), 5.84 (t, 2HiOCH ₂ -), 3.02 (dd, IH, '8 Hz), 2.47 (d, IH, 2Hz), 1.97 (d. IH, 8 Hz ) - phenyl protons; 2.19 (i.e. IH, 2 Hz), 1.74 (bs, IH), pyridyl protons.

Example 14:

The post-em herbicidal effect on the grasses (GR) Setaria vividis, Echinochloa oryzoides, Ech. phyllopogon, sorghum bicolor and. Av.ena fatua and on the broad-leaved weeds (BL) Ipomoea purpurea ,. Brassica juncea, Brassica kaber, Glycine max and Abutilon theophrasti was investigated for the compounds a, b, c, d, e and f (below) by spraying seedlings with a water / acetone (1: 1) solution of the test substance containing 1 % surface-active substance with an application amount equiyalent Π kg / h yes. The evaluation was carried out 2 weeks after treatment. Of the The mean value of the test results is shown in Table C in% damage.

Test substances :

a) N-met'hoxy-N-methoxycarbonylmethyl -2-nitro-5- (2-chloro-4-tri f 1 uormethyl phenoxy) aniline.

b) N-methoxy-N-methoxycarbonylmethyl-2-nitro-5- (3-chloro-5-trifluoromethyl -2-pyridyl oxy) ani 1 i η.

c) N-methoxy-N-2-methoxyethoxycarbonylmethyl-2-nitro-5- (3-chloro-5-trifluoromethyl-2-pyridyloxy) anion.

d) N-methoxy-N-isobutoxycarbonylmethyl-2-nitro-5- (2-chloro-4-trifluoromethylphenoxy) aniline.

ιυο ι

'W- 133-0583

e) N-methoxy-N-isopropoxycarbonylmethyl-2-nitro-5- (Z-chloro-4- · trifluoromethylphenoxy) ani1 in.

f) N-methoxy-N-isopropoxycarbonylmethyl-2-nitro-5- (3-chloro-5-trifluoromethyl-2-pyridyloxy) ani1iη.

The pre-em herbicidal effect of compounds a, b, c, d, e and f was measured on the above grasses and broad-leaved weeds (with the exception that Glycine max was replaced by Solanum spp.) By watering the soil after sowing a 17% aqueous solution containing 0.17 % surface-active substance and the test substance with an application rate corresponding to 11 kg / ha. The evaluation took place 2 weeks after treatment. The mean value of the test results is given in Table C in% control.

With pre-em treatment, each of the above test substances has a good one Selectivity in corn, cotton, soy, barley and wheat.

I. Test substance 1 _—, ■? .. »* .- ..
- ** % GR damage Pre GR BL a Table C. post 100 ■ 90 • 100 b 100 · BL 100 100 C. 100 · 99 99 100 d 97 100 100 100 e 100 95 100 - 100 f 72 100 100 100 82 100

- 25 "-. 133-0583

Further experiments with test substance b gave a mean I ₇₀ (where I ₇₀ corresponds to the application amount which allows a 70 % herbicidal effect).

After pre-em application of 1.19 kg / ha against GR and about 0.64 kg / ha against BL.

After post-em application of less than 0.05 kg / ha against GR and of less than 0.07 kg / ha against BL.

Claims (7)

I UJ I / 133-0583 Claims; r \ '1, J Process for the preparation of a compound of the formula I, Jt , N-OR where M is CH or N,
t stands for 0, 1 or 2,
X stands for O or S, Y and Z, independently of one another, represent H, C-, g-alkyl, C | _g-alkoxy, CigHaloalkyl, C ^ gHaloalkoxy, halogen, CN and NO ₂ , R for C 1 -C 4 alkyl, C ₂ -C 4 alkenyl, C ₂ -C 4 -alkynyl, C 1 -C 4 haloalkyl, C ₂ -C 4 haloalkenyl, C ₂ -C 4 haloalkynyl, C _2-8 (alkoxyalkyl), C ₂ -C (alkylthioalkyl), C _3-3 cycloalkyl, phenyl-C ₁ _ ₈ alkyl, or represents one of the meanings given below for R '; R ¹ for H ,. or a group A; A for CN-C ₁ _g-alkyl, (CHR ¹ ^ -COOR ² , (CHR ³ ) _n -C0R ⁴ , (CHR ³ ) SO ₂ -R ⁴ , (CHR ⁵ ) _n , -O-CO-R ⁶ , ( CHR ⁹ ) _n , -C0-0-CR ¹⁰ R ¹¹ -C00R ¹ , (CH ₂ ) _nl -W- (CH ₂ ) _nll -WR ¹³ or C0-CHR ¹⁴ -0R ¹⁵ ; R "represents NO ₂ , NH ₂ , CN or Cl, R ^{1 is} H, C ^ galkyl, C ^ galkoxy or C ^ galkylthio, - £. 133-0583 R ² and R ¹² .for H, a metal cation, C _1-8 alkyl, C ₂ _gAlkenyl, C ₂ _gAlkynyl, C ₂ _-, ₀ (alkylthioalkyl), C ₂ _ ₁₀ (alkoxyalkyl). .C ₁ ^ hydroxyalkyl, C ₂ ^ -, _Q (alkylsulfinyl alkyl), C _2- , _Q A1 kylsulfonylalkyl, substituted or unsubstituted phenyl, C ₃ "cycloalkyl, C _1-8 haloalkyl, C _3-8 (alkoxyalkoxyalkyl) , C-j_gAlkylamino, di (C _1-8 Al kyl) ami no, C _3-3 CyClOaIkyl-C _1-3 -alkyl, a saturated 3-8-membered heterocyclic group with one or 2 heteroatoms selected from 0 and Nj substituted or unsubstituted benzyl or represent a group N = C (R ⁸ ) ₂ ; R ³ and R ^{14 represent} H or C _1-3 alkyl; R ⁴ is C _1-8 alkyl, C ₂ _gAlkenyl, C _1-3 alkylthio, C _1-3 Alkylami no, di (C, gAlkyl) amino, C _3-3 cycloalkyl, C _1-8 haloalkyl, substituted or unsubstituted phenyl Substituted or unsubstituted benzyl, substituted or unsubstituted C IC Anilino or the group CHR-COOR, R and R independently of one another represent H or C -, _ o-alkyl; R ^{6 represents} C _1-8 alkyl, C _3-3 (alkoxyalkyl), C _3-3 cyClOaIkyl, C _1-3 haloalkyl, or substituted or unsubstituted phenyl; or R and .R together stand for C _2- ^ alkylene or C _2- ^ alkenylene, R ⁸ and R ¹³ stand for C ₁ ^ ₈ alkyl, R, R und.R independently of one another represent H, C _1-3 alkyl, C _1-3 AlkOXy or C _1-8 alkylthio, R ^{15 represents} substituted or unsubstituted phenyl or substituted or unsubstituted phenoxyphenyl, η stands for 0, 1 or 2, n 'and n ", independently of one another, stand for 1 or 2 and · W. and W, independently of one another, represent 0 or S, 133-0583 characterized in that one a) the activated NQ _? -Group in the 2-position of a 4-substituted 1,2-diN0 ₂ benzene compound of the formula II Y, '/ W- ^χ - <\ Λ-ΝΟ in which X, Y, Z, M and t have the above meanings through an alkoxyamino group of the formula III NH-OR III where R has the above meaning, substituted, and optionally, in a suitable order, the alkoxyamino group introduced in this way by a group A, which has the above meaning, N-substituted and / or those in the ortho position. the introduced alkoxyamino group permanent N0 _? -Group hydrogenated to an NHp group, and / or the latter NH ₂ -GrUpPe replaced by Cl or a CN group and / or an al! Carboxyl ester group hydrolyzed to the free carboxyl group or converted to a salt thereof, or b) to compounds of the formula Ia Yes (V Vx ^v "" Z VrM ' - 2Ϊ- ' 133-0583 in which X, Y, Z, M ", t, R and R ^{1 have the} above meanings, obtained by adding a compound of the formula Ib Ib wherein X, Y, Z, M, t and R have the above meaning, through a group A, which has the above meaning, N-substituted. 2. A compound of formula I as defined in claim 3. A compound according to claim 2 of the formula Ic ^{1 Y} NR'-OR -R "'Ic ¹ wherein Y, Z, M, R, R ¹ and R "have the meaning given in claim 1. 4. A compound according to claim 3, wherein Y for H 'or Cl, Z for Cl or CF ₃ , R for C ^ alkyl, R ¹ for CH ₂ -COOR ² , R ² for C _1-4 alkyl or C-j__ ₄ A1 koxy-C-j_ ₄ alkyl and R ″ stands for NO ₂ . -Xf- ■ ■ 133-0583 5. 'A compound according to claim 4 of the formula a) N-ynethoxy-N-methoxycarbonylmethyl-2-nitro-5- (2-chloro-4-trifluoromethylphenoxy) ani1 in, b) N-methoxy-N-isobutoxycarbonylmethyl-2-nitro-5- (2-chloro-4-trifluoromethylphenoxy) aniline, c) N-methoxy-N-methoxycarbonylmethyl-2-nitro-5- (3-chloro-5-tri fluoromethyl-2-pyridyloxy) ani1i η, or d) N-methoxy-N-2-methoxyethoxycarbonylmethyl-2-nitro-5- (3-chloro-5-trifluoromethyl-2-pyridyloxy) aniline. 6. A herbicide containing a compound according to any one of claims 2 to 5 and an agriculturally acceptable one Diluents. 7. Method for combating weeds, characterized in that that a herbicidally effective amount of a compound according to one of the claims is added to the weeds or their type of growth 2 to 5 applied.