CA1198114A - Anilines and their use - Google Patents

Abstract

Abstract:
Substituted phenoxyanilines and pyridyloxyanilines, and the use thereof for the control of weeds. The novel compounds have the formula

Description

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Case 133-0583 Novel Phenoxyanilines, Pyridyloxyanilines, Phenylthioanilines and Pyridylthioanilines and their use for the control of weeds This invention relates to certain substituted phenoxyanilines and pyridyloxyanilines, intermediates therefor, and the use of said compounds for the control of weeds.
The novel compounds Gf the present invention are represented by the following formula I, R' ~-OR
~ X ~ R" I

wherein M is CH or N, t is 0, 1 or two, X is oxygen or sulfur, each of Y and Z is, independently, selected from hydrogen, Cl 8alkyl, Cl 8alkoxy, Cl 8haloalkyl, Cl 8haloalkoxy, halogen, cyano and nitro, R is Cl 8alkyl, C2 8alkenyl, C2 8alkynyl, Cl 8haloalkyl, C2 8haloalkenyl, C2 8haloalkynyl, C2 lO(alkoxyalkyl)9 C2 1O(alkylthioalkyl), C3 8cycloalkyl, phenyl-Cl 8-alkyl, lS or independently selected from the values of R';
R' is hydrogen or a group A which is cyano-Cl 8alkyl or -(CHRl)n-COOR2l or -(CHR3)n-Co-R , or -(CHR3)n-So2-R4, or -(CHR5)n,-o-Co-R6, or -(CHR9)n,-CO-O-CRlORll-CO-OR12, or -(CH2)n,-W-(CH2)nu-W'-Rl3 , or -CO-CHR 4-oR 5 ;
R" is nitro, amino, cyano or chloro;
Rl is hydrogen, Cl 8alkyl, Cl 8alkoxy or Cl 8alkylthio;
each of R2 and R12 is hydrogen, metal cation, Cl 8alkyl, C2 $alkenyl, C2 8alkYnYl- C2 10(alkYlthioalkyl), C2 lO(alkoxyalkyl)~
1-8 ydroxyalkyl, C2 l0(alkylsulfinylalkylJ~ C2 lO(alkyl-sulfonylalkyl), C3 8cycloalkyl~ Cl 8haloalkyl, C3 8(alkoxy-;~!

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-2- 133-0583 alkoxyalkyl), Cl 8alkylamino, di(Cl 8alkyl)amino, C3 8cyclo-alkyl-Cl 3alkyl, a saturated 3-8 membered heterocyclic group having 1 or 2 heteroatoms selected from 0 or N, N=C(R8)2~ or unsubstituted phenylor benzyl or phenyl or benzyl substituted at one, two or three of the ring carbon atoms with a group selected from Cl 8alkyl, C1 8haloalkyl, C1 8alkoxy, C2 8alkenyl, C2 8haloalkenyl, C2 8alkenyloxy, halogen, nitro, cyano or Cl 8alkylthio;
each of R and R is hydrogen or C1 8alkyl;
R is Cl 8alkyl, C2_8alkenyl, Cl 8alkylthio, Cl 8alkylamino, di(C1 8alkyl)amino, C3 8cycloalkyl, Cl 8haloalkyl; the group R5 o -CH-C-OR16 ; or unsubstituted phenyl, benzyl or anilino, or phenyl, benzyl or anilino substituted at one, two or three of the ring carbon atoms with a group selected from Cl 8alkyl, C1 8-haloalkyl, C1 8alkoxy~ C2 8alkenyl, C2 8haloalkenyl~ C2 8-alkenyloxy, halogen, nitro, cyano or Cl 8alkylthio~
each of R5 and R16 is hydrogen or Cl 8alkyl;
R6 j5 Cl 8alkyl, C2 8(alkoxya!kyl), C3 8cycloalkyl, Cl_8haloalkyl, unsubstituted phenyl or phenyl substituted at one, two or three of the ring carbon atoms with a group selected from Cl 8alkyl, 1-8 Y , C1 8alkoxy~ C2 8alkenyl, C2 8haloalkenyl C
alkenyloxy, halogen, nitro, cyano or C1 8alkylthio; or together with R forms a C2 4alkylene or a C2 4alkenylene group, each of R and R is C1 8alkyl; 5 each of R9, R and R 1 is independently selected from hydrogen, Cl 8alkyl, Cl 8alkoxy, or Cl 8alkylthio;
R 5 is unsubstituted phenyl or phenyl substituted at one, two or three of the ring carbon atoms with a group selected from Cl 8-alkyl, Cl 8haloalkyl, Cl 8alkoxy, C2 8alkenyl, C2 8haloalkenyl, C2 8alkenyloxy, halogen, nitro, cyano or C1 8alkylthio; or unsubstituted phenoxyphenyl or a phenoxyphenyl group substituted 8~

3_ 133-0583 at one, two or three of the phenoxy ring carbon atoms with a group selected from Cl 8alkyl, Cl 8haloalkyl, Cl 8alkoxy7 Cl 8-haloalkoxy, C2 8alkenyl, C2 8haloalkenyl9 C2 8alkenyloxy, halogen, nitro, cyano or Cl 8alkylthio;
n is 0, 1 or 2;
n' and n",independently, are 1 or 2; and each of W and W' is, independently, oxygen or sulfur.

The term C2 8alkenyl refers to an unsaturated C2 ~hydrocarbon group having one or two ethenylenic honds The term C2 8alkynyl refers to an unsaturated C2 8hydrocarbon group having one or two acetylenic bonds.
The terms Cl 8haloalkyl, Cl 8haloalkoxy, C2 8haloalkenyl a d C2 8haloalkynyl refer to Cl 8alkyl, Cl 8alkoxy, C2 8alkenyl anc C2 8alkynyl groups resp. substituted with one to three halogen atoms.
Examples of suitable metal cation significances of R2 and R12 include the cations of alkali and alkaline earth metals such as Li, Na, K, Ca9 Ba, Sr and Mg.
R is preferably Cl 8alkyl, more preferably Cl 4alkyl and particularly CHl ~

Aliphatic hydrocarbyl substituents of the compounds of formula I have preferably not more than 4 carbon atoms, alkyl substituents, or alkyl moieties of substituents of the compounds of ~ormula I have more preferably 1 or 2 particularly 1 carbon atom;suitable examples of alkenyl and alkynyl substituents of the compounds of formula I are i.a. CH2 CHaCH2 and CH C-CH
A suitable example of a heterocyclic group R2 or R12 is 2-tetrahydro-furyl.
A suitable example of a C3 8cycloalkyl-C1 3alkyl group R2 or R12 10 is cyclopropyl-ethyl.
The term halogen refers to F, Cl, Br and I, especially F and Cl.
The invention also provides processes for producing a compound of formula I comprising a) substituting the activated N02 group in the 2-position of a 4-substi-tuted-1,2-dinitroben~ene compound of formula II

z ~ ~ 2 II

wherein X, Y, Z9 M and t are as defined above, by an alkoxyamino group of formula III9 NH-CR III
wherein R is as defined above, followed, where desired, in a~propriate onder, by N-substitution of the thus introduced alkoxyamino group by a group A, which is as defined for R' with the exception of H, and/or hydrogenation of the N02 group in the ortho position to the introduced alkoxyamino group to a NH2 group, and/
or substitution of the lattPr NH2 group by Cl or a CN group, and/or hydro-lysation of any carboxylic acid ester group to the free carboxyl group 25 or its salt form;

~8~4 ~5~ 1 33-0583 b) or obtaining a compound of formula la Yt A-OR
~X~ No2 Ia wherein X, Y, Z, M, ~, R and A are as defined above, by N-substituting a compound of formula Ib Y$ NH -OR
~ X ~ No2 Ib wherein X, v, z, M, t and R are as defined above by a group A, which lS as defined above by N-alkylation techniques.
A suitable reaction scheme is as follows:

Yt NHOR yt NR'-OR
Formula II ~ ~ X ~NO A ~ ~ X ~ No2 Ib \ ~ Ia Yt ,~IR ' -OR \~ Yt PIR ' -OR
~, 1 )HCl+HN02 rt~ ~( X ~ ~Cl(or CN) ~ (~ '~ X ~ ~ NH
z/~= M ~ 2 ) Cu2C 12 or z'~ M' ~ 2 Id Cu2(CN)2 Ic -5a- 133-0583 Depending on the significance of the substituents other sequences may be more appropriate.
The above syntheses of the compounds of formula Ib is conveniently effected by using the compound of formula III in salt fcrm, e.g. as hydro-5 chloride, and in the presence of a base such as K2C03.
A suitable reaction medium is an organic solvent which is inert underthe reaction conditions, such as CH2C12, tetrahydrofuran (THF) or N,N-di-methylformamide (DMF). The reaction can be effected at room temperature.
The N-substitution of a compound of formula Ib can be effected 10 according to N-alkylation techniques known in the art. Alkylating agents suitable for use in the alkylation reaction of the invention are e.g. compounds of formula IV, A-Hal IV
wherein ~ is the group as defined above and Hal is halogen, such as Cl or Br, 15 reactive derivatives thereof, such as acrylates, anhydrides etc.
Where a compound of formula IY is used as alkylating agent~ the reaction is conveniently effected in an organic solvent which is inert under ~h~ reaction conditions such as acetone, 2-butanone, CH2C12, benzene or DMF. The presence of a base such as triethylamine9 K2C03, pyridine or 20 NaH may be advantageous. A suitable reaction temperature is room temperature `~:f -6- 133~0583 or higher temperature. AlternatiYely, the compound of formula Ib can also be reacted in its N-metal salt form (see e.g. Example 1).
The hydrogenation of the above compounds of formula Ia to compounds of Ic (Reaction scheme) can be effected by selective hydrogenation of the N02 group to the amino group, in a manner known per se, e.g. with the aid of NaBH4 or analogous hydrogenation means.
The conversion of compounds of formula Ic to compounds of formula Id may be effected by any manner known forthe substitution of an aromatic amine by Cl or a CN group. An example of a suitable reaction is the 10 diazotation of the amino group according to known methods e.g. with the aid of HCl and NH02 asi.a. described in Org. Synth. Coll. Vol. 1:
514 (1932),and subsequent reaction of the diazo salt with cuprous cyanide or cuprous chloride according to Sandmeyer.
The hydrolysation of any carboxylic acid ester gro~p present in the 15 compounds of formula I to a free carboxylic group can be effected in a manner known per se. e.g. with the aid oF a base such as NaOH in a suitable solvent which is inert under the reaction conditions such as methanol. Such free carboxylic acid can be isolated as such or as salt (alkali or alkaline earth metal), to which the carboxylic acid can be 20 converted by reaction with a strong base, e.g. a metal hydride.
The compounds of formula I may be recovered frorn the reaction mixture in which it is formed by working up according to es~ablished procedures.
Insofar as the production of starting material is not described herein, these compounds are known or may be produced in accordance with 25 known processes or in a manner analogous to processes described herein or to known processes.

The compounds of formula L are useful for the control of weeds, using pre- and/or post-emergent treatments. The compounds can be applied in the form of dusts, granules, solutions~ emulsions, wettable powders, flowables and suspensions. Application of a compound of the present invention is made according to conventional procedure to the weeds or their locus using an herbicidally effectiYe amount of the compound, usually from about 100 9 to 10 kg/ha.
The compounds of the present invention have favourable broad spectrum herbicidal activity on both broad leaf plants and the grassy weeds or 10 graminaceous weeds. The optimum usage of a compound of the present invention is readily determinable by one of ordinary skill in the art using routine testing such as green house testing and small plot testing.
However, in general, satisfactory results are usually obtained with the compound is applied at a rate in the range of from 0.1 to 5 kg/ha, 15 preferably from about 0.2 to 4 kg/ha, more preferably from 0.5 to 3 kg/ha, the application being repeated as necessary.
The compounds of the invention are relatively less toxic towards crops than towards weeds. Selective herbicidal activity is i.a. observed in cereals such as wheat, barley and rice, in cotton, in soybean and 20 particularly in corn (maize). The compounds are therefore ;ndicated for use as selective herbicides in a crop locus.
The term "herbicide", as used herein, refers to an active ingredient which modifies the growth of plants because of phytotoxic or plant growth regulating properties so as to retard the growth of the 25 plant or damage the plant sufficiently to kill it.
Preferred compounds have one or more of the following features:

3; 13~

- 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-CF3, preferably p-CF3 - R' is (CHRl)n-COOR2, C0-CH2-COOC1 4alkyl, C0-C1 4alkyl, - n is 0 or 1, more preferably 1, - R is H or CH3, 1-~ Y , 1-2alkyl-o(cH2)l 2~ CH3-S-(CH2)2~ CH3~S~(CH2) CH3S02CH2CH2, benzyl, cyclopropyl-CH2CH2, Cl-CH2CH27 CH2-CH-CH29 CH2-C--CH or 2-tetrahydrofuryl and is more preferably CH3, - X is O
- R is CH3 R iS CH2 COOCH3 - R" is N02 The compounds of formula I are conveniently employed as herbicidal compositions in association with agriculturally acceptable diluents.
Such compositions also form part of the present invention. They may contain, aside from a compound of formula I as active agent, other 20 active agents, such as herbicides. They may be employed in either solid or liquid forms e.g. in the fonm of a wettable powder, an emulsion concentrate, a water dispersible suspension concentrate ~"flowable"), a dusting powder, a granulate, a delayed release form, incorporating conventional diluents. Such compositions may be produced in conventional 25 manner, e.g. by mixing the active ingredient with a diluent and optionally other formulating ingredients such as surfactants.
The term diluents as used herein means any 1iquid or solid agricul-turally acceptable material which may be a~ded ~o the act;ve consti~uent to bring it in an easier or improved applicable form, respectively to a 30 usuable or desirable strength of activity. It can for example be talc, kaolin, diatomaceous earth, xylene and water.

~9~ 133-0583 Particularly formulations to be applied in spraying forms such dS
water dispersible concentrates or wettable powders may contain surfactants such as wetting and dispersing agents, e.g. the condensation product of formaldehyde with naphthalene sulphonate, an alkylaryl-sulphonate, a lignin sulphonate, a fatty alkyl sulphate, an ethoxylatedalkylphenol and an ethoxylated fatty alcohol.
In general, the formulations include from 0.01 to 90YO by weight of ac~ive agent from 0 to 20% by weight of agriculturally acceptable surfactant and 99.99 to 10% by weight (solid or liquid) diluent(s), the active agent consisting either of at least one compound of formula I or mixtures thereof with other active agents. Concentrate forms of composi-tions generally contain between about 2 and 90%, preferably between about 5 and 70% by weight of active agent. Application forms of formula-tion may for example contain from 0.01 to 20~ by weight, preferably from 0.01 to 5'~ by weight of active agent.
The following examples are proYided to illustrate the practice of the present invention. Temperatures are given in degrees centigrade.
"RT" means room temperature. "THF" stands for tetrahydrofuran. "TLC"
means thin layer chromatography. Parts are by weight.

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Formulation Exarnple 1: Wettable powder 25 Parts of a compound of formula I, are ground with 3 parts of lauryl sulphate, 5 parts sodium lignin sulphonate, 22 parts of silica and 45 parts of finely divided kaolinite until the mean particle 5 size is below 5 microns. The resulting wettable powder so obtained is diluted with water before use.
Formulation Example 2: Emulsion Concentrate 25 Parts of a compound of formula I9 65 parts of xylene, 10 parts of the reaction product of an alkylphenol with ethyleneoxide and calcium-10 dodecylbenzene sulphonate are thoroughly mixed until a homogeneous solutionis obtained. The resulting emulsion concentrate is diluted with water before use.
EXAMPLE 1: N-Methoxy-2-nitro-5-(2-chloro-4-trifluorometh~lehenox~y2-aniline A mixture of 4-(2-chloro-4-trifluoromethylphenoxy)-1, 2-dinitrobenzene (1000 mg, 2.76 mmol), methoxyamine hydrochloride (362 mg, 5.52 mmol), potassium carbonate (762 mg, 5.52 mmol), and THF (15 ml) is stirred at RT
for 4 days. The reaction mixture is then filtered, and the filtrate is concentrated to dryness. The crude residue is taken up in ether, washed, 20 dried and evaporated to dryness to give, after purification by column chromatography, the title compound; m.p. 105 Following the procedure Example 1, reaction of the appropriate

4-(substituted phenoxy)-1,2-dinitrobenzene or 4-(substituted-2-pyridyloxy)-25 1,2-dinitrobenzene with alkoxyamine hydrochloride yields the following compounds of formula I (Table A).

Table A tX=O, R=CH3, R' = H and R" = N02) M Z Yt R
2.1 CH 4-CF3 H CH3 2.2 CH 4-CF3 2-F C~13 2.3 CH 4-C1 2-N02 CH3 2.4 CH 2-C1 6-C1 CH3 2.5 CH 4-CF3 2-C1-6-F CH3 2.6 N 4-CF3 2-Cl CH3 (1) 2.7 CH 4-C1 2-Cl CH3 10 2.~3N 3-Cl S-Cl CH3 2.9 CH 4-CF3 2-Cl C2H5 (1) nmr (CDC13) ~ 6.25 (s, 3H, NOCH3), [3.44 (dd, lH, 8 Hz), 2.90 (d, lH, 2Hz), 1.87 (d, lH, 8Hz) phenyl H], [2.17 (d, lH, 2Hz), 1.77 (d, lH, 2Hz) pyridyl H].
EXAMPLE 3 : N-Methoxy-N-methoxycarbonyl-2-nitro-5-(2-chloro-4-trifluoro methylehenoxy)aniline To a solution of N-methoxy-2-nitro-5-(2-chloro-4-tri~luoromethyl phenoxy)aniline (660 mg, 1.32 mmol) in methylene chloride (10 ml) is added, at 0, triethylamine (0.5 ml, 3.64 mmol) and methylchloroformate (0.3 ml). The resulting mixture is stirred at RT for 16 hours. The reaction mixture is poured into water and extracted with ether. The extracts are combined and washed, dried and evaporated to dryness. The crude product is purified by prep.TLC to give the title compound.
nmr (CDC13) ~ 6.24 (s, 3H, O-CH3) and 6.19 (s, 3H, C(O)OCH3).
IR (film) = 1730 cm 1 (C(O)OCH3).

EXAMPLE 4: N-Methoxy-N-methoxycarbonylmethyl-2-nitro-5-(2-chloro-4 trifluoromethylphenoxylaniline A mixture of the aniline of Example 1 (530 mg, 1.46 mmol), methyl bromoacetate (0.27 ml, 2.92 mmol), potassium carbonate (303 mg, 2.19 mmol) and acetone (10 ml) is heated under reflux for 4 hours. The reaction mixture is filtered, and the filtrate is concentrated to yield9 after purification by prep. TLC, the title compound. MS m/e 434 (M ).
EXAMPLE 5 : 2-N02-5-(2-chloro-4-trifluoromethylphenoxy)-N-methoxy-acetanilide Acetic anhydride (0.6 ml) is added to a solution of the aniline of Example 1 (500 mg, 1.38 mmol) in pyridine (5 ml). The resulting mixture is stirred at RT overnight, after which it is diluted with methylene chloride and acidified. The phases are separated, and the organic phase is washed, dried and evaporated. The crude product is purified by prep-.TLC
15 to yield the title compound.
nmr (CDC13) ~ 7.74 (s, 3H, C(O)CH3), 6.24 (s, 3H, N-OCH3).
IR (film) = 1690 cm 1 (C(O)CH3).
EXAMPLE 6 : N-Methoxy-N-2-methoxycarbonylethyl-2-nitro-5-(3-chloro-5-tri-fluoromethyl-2-eyr_dyloxy)aniline To a solution of N-methoxy-2-nitro-5-(3-chloro-5-trifluoromethyl-2-pyridyloxy)aniline (1.55 mmol) in methanol (10 ml) is added methyl acrylate (1.56 mmol) and a catalytic amount of sodium methoxide. The mixture is stirred at RT for about one hour, after which it is poured into water, acidified and extracted with ether. The combined extracts are 25 washed, dried~ evaporated to dryness and purified by prep. TLC to give the title compound.

_13 133-0583 EXAMPLE 7 : N-Methoxy-N-l-methoxycarbonyl-ethyl-2-nitro-5-(2-chloro-4-_ _ _ _ _ _ _ _ _ trifluoromethylehenox~)anlline To a solution of N-Methoxy-2-nitro-5-(2-chloro-4-trifluoromethyl-phenoxy)aniline (500 mg, 1.38 mmol) in N,N-dimethylformamide (5 ml) is added, at 0, NaH (50%; 72 mg). The resulting solution is stirred until bubbles cease, about 10 minutes, and methyl a-bromopropionate (276 mg, 1.65 mmol) is added dropwise. The mixture is stirred at RT for 6 hours and is then diluted with ether, poured into 10% aqueous HCl and extracted with ether. The combined extracts are washed, dried and evaporated to dryness to give an oily residue which is purified by prep. TLC to give the title compound.
nmr (cDcl3)r 8.45 (d, 3H, NCHCH3, 6.67 (s, 3H, COOCH3), 6.44 (s, 3H, NOCH3) NOCH3) 5.90 (q, lH, NCHCH3).

Following the procedure of one of the Examples 3 or 4, reaction of the appropriate compound of formula I, wherein R' is H with an halide yields the following compounds of formula I (Table B).
Table B (X is 0, and R" is N02) Cpd. M Z Yt R R' 1 CH4-CF3 2-Cl CH3 CH2CH2COOCH3 2 CH4-CF3 2-Cl C2H5 CH2COOCH3 3 CH4-CF3 2-Cl CH3 CH2COOt-C4Hg (1) 4 CH4-CF3 2-Cl CH3 CO CH2-CO-OC2H5 (2) N5-CF3 3-Cl CH3 CH2COOCH3 MS m/e 435 (M+) 6 N5-CF3 3-Cl CH3 CH2COOiC3H7 MS m/e 463.8 (M+) 7 N5-CF3 3-Cl CH3 CH2COOCH2CH20CH3 MS m/e 479-8 (M ) F3 3-Cl CH3 CH2-COO-CH2CH25CH3 9 N5-CF3 3-Cl CH3 CH2COO~CH2CH(CH3)2 F3 3-Cl CH3 CH2COO-(CH2)20CH2CH3 Cpd. M Z Yt R R' 11 N F3 3-Cl CH3 CH2C00-CH2CH250CH3 12 CF3 3-Cl CH3 CH2-C00-CH2CH2S02CH3 13 N5-CF3 3-Cl CH3 CH2-C00-CH2 14 N5-CF3 3-Cl CH3 CH2-COO-CH2CH2~
N 3 3-Cl CH3 CH2-C00-CH2CH=CH2 16 N5-CF3 3-Cl CH3 CH2-C00-CH2CH2Cl 17 N F3 3-Cl CH3 CH2-C00-CH2C-CH
18 N5-CF3 3-Cl CH3 CH2-C00 ~
19 N5-CF3 3-Cl CH3 CH(CH3)-C00-CH3 N5-CF3 3-Cl CH3 CH(CH3)-C00-CH2CH20CH3 21 CH4-CF3 2-Cl CH3 CH2-C00-CH(CH3)2; MS m/e 462 22 CH4-CF3 2-Cl CH3 CH2-C00-CH2CH(CH3)2; MS m/e 476 23 CH4-CF3 2-Cl CH3 CH2-C00-CH2CH20CH3; MS m/e 480 24 CHCF3 2-Cl C~13 CH2-C00-CH2CH2SCH3 CHCF3 2-Cl CH3 CH2-C00-CH2CH2SOCH3 26 CHCf3 2-Cl CH3 CH2-C00-CH2CH2S02CH3 27 CH4 CF3 2 Cl CH3 CH2 C00 CH2CH CH2 28 CH4 CF3 2 Cl CH3 CH2 C00 CH2CH2Cl 29 CH4-CF3 2-Cl CH3 CH2C-CH2 ~
CH4-CF3 2-Cl CH3 CH(CH3)-C00-CH3 31 CH4-CF3 2-Cl CH3 CH(CH3)-C00-CH2CH(CH3)2 32 CH4-C1 2-Cl CH3 CH2COOCH3 33 CH4-C1 2-Cl CH3 CH2CCH2CH2CH3 34 N5-C1 3-Cl CH3 CH2COOCH3 N5 Cl 3 Cl CH3 CH2 COOCH~CH20CH3 36 N5 CF3 3 Cl CH3 CH2 C00CH2CH2iC3H7 37 NCF3 3-Cl CH3 CH2-coocH2cH2tc4H9 3~

-15- 133-05~3 38 N 5 CF3 3 Cl CH3 CH2 CnG~I9 39 N 5-CF3 3-C1 CH3 CH(CH3)-COOCH3 N 5-CF3 3-Cl CH3 CH(CH3) COOCH2CH(CH3)2 (1) analogous to Example 4, in 2-butanone as solvent; nmr (CDC13)~8.54 (s,9H, C(CH3)3), 6.40 (s,3H, N-OCH3), 6.10 (s,2H, N-CH2-);
IR (film) = 1740 cm 1 (C(O)O) (2) analogous to Example 3, nmr (CDC13)~ 8.74 (s, 3H, OCH2CH3), 6037 (s, 2H, C(O)CH2C(0)), 6.24 (s, 3H, N-OCH3), 5.84 (q, 2H, 0C~2 CH3).
IR (film) = 1695, 1740 cm~l (C(O)CH2C(O)O).

N-methoxy-N-methoxycarbonylmethyl-2-nitro-5-(2-chloro-4~trifluoro-methylphenoxy)aniline is treated with 10% NaOH (10 ml) in methanol (10 ml) at RT for about 30 minutes. The mixture is then poured into water and repeatedly extracted with ether. The extracts are combined to give the 15 free acid.
The above-prepared acid is stirred with NaH (59 mg, 50% oil) and anhydrous ether (4 ml) at RT for one hour. Solvent is removed, and the solid is washed with pentane and dried under vacuum to yîeld the corres-ponding sodium salt.

Following the procedure of Example 9, the free acid of N-methoxy-N-methoxycarbonylmethyl-2 nitro-5-(3-chloro-5-trifluoromethyl-2-pyridyloxy)-aniline is prepared and is then treated with NaH to give the corresponding sodium salt.

EXAMPLE 11 : N-Methoxy-N-methoxycarbonylmethyl-2-amino-5-(2-chloro-4-tri-_ _ _ _ _ ~ _ fluoromethylehenoxx~aniline _ .. _ _ _ _ To a solution of N-methoxy-N-methoxycarbonylmethyl-2-nitro-5-(2-chloro-4-trifluoromethylphenoxy)aniline (868 mg) and anhydrous stannous chloride (2.25 9) in methanol (140 ml) is added, at 60, sodium borohydride (30 mg) in methanol over a period of about 20 minutes. After addition, the reaction mixture is stirred for about 30 minutes, then cooled to 5-10 and water is added, followed by neutralization with dilute NaOH. The methanol is evaporated off and the aqueous solution is extracted with 10 methylene chloride. The extracts are combined, washed, dried and evaporated to dryness to give the title compound.

Following the procedure of Example 11, N-methoxy-N-methoxycarbonyl-methyl-2-amino-5-(3-chloro-5-trifluoromethyl-2-pyridyloxy)aniline is 15 prepared.

Each of the compounds of Example 11 and 12 is diazotized following the procedure described in Org. Synth. Coll. Vol 1: 514 (1932). The resulting diazo salts are treated with cuprous cyanide (1.2 eq.) in 20 benzene-water solution to give, respectively, 13.1 N-methoxy-N-methoxycarbonylmethyl-2-cyano-5-(2-chloro-4-trifluoro-methylphenoxy)aniline 13.2 N^methoxy-N-methoxycarbonylmethyl-2-cyano-5-(3-chloro-5-trifluoro-methyl-2-pyridyloxy)aniline By reacting each of the diazo salts with cuprous chloride (1.2 eq.), there is prepared 13.3 N-methoxy-N-methoxy-carbonylmethyl-2-chloro-5-(2-chloro-4-trifluoro-methylphenoxy)aniline.

13.4 N-methoxy-N-methoxycarbonylmethyl-2-chloro-5-(3-chloro-5-trifluoro-methyl-2-pyridyloxy)aniline.

Post-emergence herbicidal activity on the grasses (GR) green foxtail, watergrass, shattercane and wild oats and on the broadleafs (BL) annual morning glory, mustard, soybean and velvetleaf was tested for the test compounds a, b, c, d, e and f (below)by spraying seedlings with a solution of water/acetone (1:1), surfactant (1%) and test compound at a rate equivalent to 11 kg/ha. Scoring was made two weeks after treatment. The 10 average activity, in percent control, is given in Table C.
TEST COMPOUNDS
a) N-methoxy-N-methoxycarbonylmethyl-2-nitro-5-(2-chloro-4-trif1uoromethyl-phenoxy)aniline.
b) N-methoxy-N-methoxycarbonylmethyl-2-nitro-5-(3-chloro-5-trifluoro-methyl-2-pyridyloxy)aniline.
c) N-methoxy-N-2-methoxyethoxycarbonylmethyl-2-nitro-5-(3-chloro-5-trifluoromethyl-2-pyridyloxy)aniline.
d) N-methoxy-N-isobutoxycarbonylmethyl^2-nitro-5-(2-chloro-4-trifluoro-methylphenoxy)aniline.
20 e) N-methoxy-N-isopropoxycarbonylmethyl-2 nitro-5-(2-chloro-4-trifluoro-methylphenoxy)aniline.
f) N-methoxy-N-isopropoxycarbonylmethyl-2-nitro-5-(3-chloro-5-trifluoro-methyl-2-pyridyloxy)aniline.

Pre-emergence herbicidal activity of test compounds a, b, c, d, e and f was tested on the above grasses and broadleafs (except that night-shade was substituted ~or soybean) by drenching the soil, after the seeds were planted, with a solution of water (17%), surfactant (0.17%) and the test compound at a rate of 11 kg/ha. Scoring was made two weeks after treatment. The average activity, in percent control, is given in Table C.
When applied as a pre-emergence herbicide, each of the above test compounds exhibits good selectivity in corn, cotton, soybeans, barley and wheat.

TABLE C
% Herbicidal Control Post Pre Test Compound GR BL GR BL
a 100 99 90 100 b 100 100 100 100 c 100 95 99 100 d 97 100 100 100 e 100 82 100 100 f 72 100 100 100 Further evaluation of Test compound (b) indicated an average I70 (I70 corresponding to an application rate allowing a herbici~al efficacy of 70%) after pre-em application o~ 1.19 kg/ha against GR and of ca. 0.64 kg/ha against BL 5after post-em application of less than 0.05 kg/ha against GR and ofless than 0.07 kg/ha against BL.

_19 _ A selection of the compounds of the preceding Ex~mples is further characterised as follows:
Example NMR (CDC13) ~C

4 6.40 (s, 3H, N-OCH3)9 6.25 (s, 3H, OCH3), 5.g7 (s, 2H, NCH2), 3.33 (dd, lH, 8 Hz), 2.80 (d, lH, 8 Hz), 2.70 (d, lH, 2 Hz), 2.43 (dd, lH, 8 Hz)9 2.30 (s, lH, 2 Hz), 2.03 (d9 lH, 8 Hz) - aromatic protons.
8.5 6.37 (s, 3H, N-OCH3), 6.25 (s, 3H, COOCH3), 5.97 (s~ 2H, NCH2~9 3.04 (dd, lH, 8 Hz), 2.50 (d, lH, 2 Hz)9 2.04 (d, lH, 8 Hz) -phenyl protons;
2.07 (d, 1 H9 2 Hz), 1.80 (s, lH, 2 Hz) - pyridine protons.
8.6 8.72 (d, 6H, 6 Hz, CH(CH3)2), 6.37 (s, 3H, N-OCH3), 4.9 (m, lH9 OCH(CH3)2), 3.04 (dd, lH, 8 Hz), 2.50 (d, lH, 2 Hz), 2.04 (d, lH, 8 Hz) - phenyl protons;
2.07 (d, lH, 2 Hz), 1.80 (s, lH, 2 Hz) - pyridine protons.
8.7 6.64 (s, 3H, -OCH3), 6.44 (t, 2H, e-O-CH2-CH2-0), 6.40 (s, 3H, NOCH3), 5.97 (s, 2H, NCH2), 5.70 (t, 2H, o C-O-CH2-CH20), 3.04 (dd, lH, 8 Hz), 2.50 (d, lH, 2 Hz), 2.04 (d, lH, 8 Hz) - phenyl protons; 2.07 (d, lH, 2 Hz), 1.80 (s, lH, 2Hz) - pyridine protons.
8.8 7.87 (s, 3H, SCH3), 7.39 (t, 2H9 -CH2S-), 6.40 (s, 3H, N-OCH3),

5.97 (s, 2H, NCH2-), 5.70 (5, 2H, OCH2-), 3.04 (dd, lH, 8 Hz), 2.50 (d, lH, 2 Hz), 2.04 (d, lH, 8 Hz) - phenyl protons;
2.07 (d, lH, 2 Hz), 1.80 (bs, lH) - pyridyl protons.
8.9 9.08 (d, 6H, 6 Hz, CH(CH3)2), 8.20 (m, lH, CH(CH3)2), 6.40 (s, 3H, N-OCH3), 6.09 (d, 2H, 6 Hz, o C-O-CH2), 5.97 (s, 2H9 N-CH2), 2.94 (dd, lH, 8 Hz), 2.54 (d, lH, 2 Hz)), 1.95 (d, lH, 8 Hz) - phenyl protons; 1.98 (d, lH, 2 Hz), 1.70 (bs, lH) - pyridyl protons.

Example NMR ~CDC13) ~C
8.13 ~.40 (s, 3H9 N-OCH3)~ 5.90 (s, 2H~ N-CH2)~ 4.84 (s, 2H~ OCH2)~
2.70 (s~ 5H~ -C6Hs)~ 3.04 (dd, lH~ 8 Hz)~ 2.50 (d, lH~ 2 Hz), 2.04 (d, lH~ 8 Hz)- phenyl protons; 2.07 (d, lH~ 2 Hz)~ 1.80 (bs, lH) ~ pyridyl protons.
8.15 6.37 (s, 3H~ N-OCH3)~ 5.97 (s, 2H~ NCH2)~ 4.75 (m, 2H~ =CH2)~
4.05 (m, lH~ -CH=)~ 3.04 (dd, lH, 8 Hz), 2.50 (d, lH~ 2 Hz), 2.04 ~d, lH~ 8 Hz) ~ phenyl protons; 2.07 (d9 lH, 2 Hz)~
1.80 (bs, lH) - pyridyl protons.
8~19 8.47 (d, 3H~ 7 Hz~ NCH(CH3)-)~ 6.37 ~s, 3H~ N-OCH3)~

6.30 (s, 3H~ COOCH3)~ 5.84 (q~ lH, NCH(CH3))a 3-30 (dd, lH~
8 Hz)~ 2.50 (d, lH~ 2 Hz)~ 1.94 (d, lH~ 8 Hz) - phenyl protons;
l.gO (d, lH~ 2 Hz)~ 1.70 )bs, lH) ~ pyridyl protons.
8.21 8-75 (d, 6H~ 6 Hz)~ CH(CH3)2)~ 6.40 (s, 3H~ N-OCH3)~ 6.04 (s~ 2H, N-CH2), 4.94 (m, CH-(CH3)2), 3.33 (dd, lH, 8 Hz), 2.80 (d, lH~ 8 Hz)~ 2.80 (d, lH, 8 Hz)~ 2.70 (d, lH~ 2 Hz), 2.43 (dd, lH, 8 Hz), 2.30 (s~ lH, 2 Hz), 2.03 (s, lH~ 8 Hz) -aromatic protons.
8.22 9.08 (d, 6H~ 6 Hz~ CH(CH3)2)~ 8.20 (m, lH~ CH(CH3)2)~ 6.40 (s, 3H~ N-OCH3)~ 6.09 (d, 2H~ 6 Hz~ OCH2-)~ 5.97 (s, 2H, NCH2-), 3.33 (dd, lH~ 8 Hz~, 2.8G (d, lH, 8 Hz), 2.70 (d, lH~ 2 Hz)~
2.43 (dd, lH~ 8 Hz)~ 2.30 (s, lH, 2 Hz), 2.03 (s, lH, 8 Hz) -aromatic protons.
8.23 6.64 (s, 3H~ -OCH3)~ 6.40 (s, lH~ N-OCH3)~ 6.44 (t~ 2H~ C~O~
CH2CH20)~ 5.97 (s, 2H~ NCH2)~ 5.70 (t~ 2H)~
C-O~CH2CH2-0)~ 3.33 (dd, lH~ 8 Hz)~ 2.80 (d, lH, 8 Hz), 2.70 (d, lH, 2 Hz)~ 2.43 (dd, lH, 8 Hz)a 2.30 (s, lH, 2 Hz), 2.03 (s, lH, 8 Hz) - aromatic protons.

Example NMR (CDC13) ~
8.34 6.37 (s, 3H, N-OCH3), 6.Z5 (s, 3H, OCH3), 5.97 (s, 2H, NCU2), 3.08 (dd, lH, 8 Hz), 2.54 (d, lH, 2 Hz), 2.04 (d, lH, 8 Hz) -phenyl protons; 2.39 (d, lH, 2 Hz), 2.07 (bs, lH~ - pyridyl protons.
8.36 9.10 (d, 6H, 6 Hz, -CH(CH3)2), 8.44 (m, 3H, -CH2CH(CH3), 6.37 (s, 3H, N-OCH3), 5.97 (s, 2H3 NCH2-), 5.84 (t, 2H, -OCH2), 3.02 (dd, lH, 8 Hz), 2.47 (d, lH, 2Hz), 1.97 (d, lH, 8 Hz) -phenyl protons; 2.19 (d, lH, 2 Hz), 1.74 (bs, lH) - pyridyl protons.
8.37 9.04 (s, 9H, C(CH3)3), 8.44 (t, 2H, -CH2), 6.34 (s, 3H, N-OCH3), 5.94 (s, 2H, NCH2-), 5.77 (t, 2H, OCH2-), 3.02 (dd, 1H, 8 Hz), 2.47 (d, lH, 2Hz), 1.97 (d, lH, 8 Hz) - phenyl protons;
2.19 (d, lH, 2 Hz), 1.70 (bs, lH) - pyridyl protons.
8.38 9.17 (t, 3H, -CH3), 8.64 (m, 4H, -CH2CH2), 6.37 (s, 3H, N-OCH3) 5.97 (s, 2H, NCH2-), 5.84 (t, 2H, -OCH2-), 3.02 (dd, lH, 8 Hz), 2.47 (d, lH, 2 Hz), 1.97 (d, lH, 8 Hz) - phenyl protons;
2.19 (d, lH, 2 Hz), 1.74 (bs, lH) - pyridyl protons.

Claims (6)

What we claim is:

1. A process for preparing a compound of formula I, I

wherein M is CH or N, t is 0, 1 or two, X is oxygen or sulfur, each of Y and Z is, independently, selected from hydrogen, C1-8alkyl, C1-8alkoxy, C1-8haloalkyl, C1-8haloalkoxy, halogen, cyano and nitro, R is C1-8alkyl, C2-8alkenyl, C2-8alkynyl, C1-8haloalkyl, C2-8haloalkenyl, C2-8haloalkynyl, C2-10(alkoxyalkyl), C2-10(alkylthioalkyl), C3-8cycloalkyl, phenyl-C1-8-alkyl, or independently selected from the values of R';
R' is hydrogen or a group A which is cyano-C1-8alkyl or -(CHR1)n-COOR2, or -(CHR3)n-CO-R4, or -(CHR3)n-SO2-R4, or -(CHR5)n,-O-CO-R6, or -(CHR9)n,-CO-O-CR10R11-CO-OR12, or -(CH2)n,-W-(CH2)n"-W'-R13 , or -CO-CHR14-OR15 ;
R" is nitro, amino, cyano or chloro;
R1 is hydrogen, C1-8alkyl, C1-8alkoxy or C1-8alkylthio;
each of R2 and R12 is hydrogen, metal cation, C1-8alkyl, C2-8alkenyl, C2-8alkynyl, C2-10(alkylthioalkyl), C2-10(alkoxyalkyl), C1-8hydroxyalkyl, C2-10(alkylsulfinylalkyl), C2-10(alkyl-sulfonylalkyl), C3-8cycloalkyl, C1-8haloalkyl, C3-8(alkoxy-alkoxyalkyl), C1-8alkylamino, di(C1-8alkyl)amino, C3-8cyclo-alkyl-C1-3alkyl, a saturated 3-8 membered heterocyclic group having 1 or 2 heteroatoms selected from O or N, N=C(R8)2, or unsubstituted phenyl or benzyl or phenyl or benzyl substituted at one, two or three of the ring carbon atoms with a group selected from C1-8alkyl, C1-8haloalkyl, C1-8alkoxy, C2-8alkenyl, C2-8haloalkenyl, C2-8alkenyloxy, halogen, nitro, cyano or C1-8alkylthio;
each of R3 and R14 is hydrogen or C1-8alkyl;
R4 is C1-8alkyl, C2-8alkenyl, C1-8alkylthio, C1-8alkylamino, di(C1-8alkyl)amino, C3-8cycloalkyl, C1-8haloalkyl; the group ; or unsubstituted phenyl, benzyl or anilino; or phenyl, benzyl or anilino substituted at one, two or three of the ring carbon atoms with a group selected from C1-8alkyl, C1-8-haloalkyl, C1-8alkoxy, C2-8alkenyl, C2-8haloalkenyl, C2-8-alkenyloxy, halogen, nitro, cyano or C1-8alkylthio;
each of R5 and R16 is hydrogen or C1-8alkyl;
R6 is C1-8alkyl, C2-8(alkoxyalkyl), C3-8cycloalkyl, C1-8haloalkyl, unsubstituted phenyl or phenyl substituted at one, two or three of the ring carbon atoms with a group selected from C1-8alkyl, C1-8haloalkyl, C1-8alkoxy, C2-8alkenyl, C2-8haloalkenyl, C2-8-alkenyloxy, halogen, nitro, cyano or C1-8alkylthio, or together with R5 forms a C2-4alkylene or a C2-4alkenylene group;
each of R8 and R13 is C1-8alkyl;
each of R9, R10 and R11 is independently selected from hydrogen, C1-8alkyl, C1-8alkoxy, or C1-8alkylthio;
R15 is unsubstituted phenyl or phenyl substituted at one, two or three of the ring carbon atoms with a group selected from C1-8-alkyl, C1-8haloalkyl, C1-8alkoxy, C2-8alkenyl, C2-8haloalkenyl, C2-8alkenyloxy, halogen, nitro, cyano or C1-8alkylthio; or unsubstituted phenoxyphenyl or a phenoxyphenyl group substituted at one, two or three of the phenoxy ring carbon atoms with a group selected from C1-8alkyl, C1-8haloalkyl, C1-8alkoxy, C1-8-haloalkoxy, C2-8alkenyl, C2-8haloalkenyl, C2-8alkenyloxy, halogen, nitro, cyano or C1-8alkylthio;
n is 0, 1 or 2;
n' and n",independently, are 1 or 2; and each of W and W' is, independently, oxygen or sulfur, which comprises a) substituting the activated NO2 group in the 2-position of a 4-substi-tuted-1,2-dinitrobenzene compound of formula II

II

wherein X, Y, Z, M and t are as defined above, by an alkoxyamino group of formula III, NH-OR III
wherein R is as defined above, followed, where desired, in appropriate order, by N-substitution of the thus introduced alkoxyamino group by a group A, which is as defined for R' with the exception of H, and/or hydrogenation of the NO2 group in the ortho position to the introduced alkoxyamino group to a NH2 group, and/
or substitution of the latter NH2 group by C1 or a CN group, and/or hydro-lysation of any carboxylic acid ester group to the free carboxyl group or its salt form;
b) or obtaining a compound of formula Ia Ia wherein X, Y, Z, M, t, R and A are as defined above, by N-substituting a compound of formula Ib Ib wherein X, Y, Z, M, t and R are as defined above by a group A, which is as defined above by N-alkylation techniques.

2. A compound of formula I as stated in Claim 1.

3. A compound according to Claim 2, of the formula Ic' Ic' in which Y, Z, M, R, R' and R" are as defined in Claim 1.

4. A compound according to Claim 3, in which R is C1-4alkyl, R' is CH2-COOR2, R" is NO2, Y is H or C1, Z is C1 or CF3 and R2 is C1-4alkyl or C1-4alkoxy-C1-4alkyl-

5. A compound of Claim 4 which is a) N-methoxy-N-methoxycarbonylmethyl-2-nitro-5-(2-chloro-4-trifluoro-methylphenoxy)aniline, b) N-methoxy-N-isobutoxycarbonylmethyl-2-nitro-5-(2-chloro-4-trifluoro-methylphenoxy)aniline, c) N-methoxy-N-methoxycarbonylmethyl-2-nitro-5-(3-chloro-5-trifluoro methyl-2-pyridyloxy)aniline, or d) N-methoxy-N-2-methoxyethoxycarbonylmethyl-2-nitro-5-(3-chloro-5-trifluoromethyl-2-pyridyloxy)aniline.

6. A method of combatting weeds which comprises applying to the locus thereof a herbicidally effective amount of a compound according to any one of Claims 2 to 4.