Note: Descriptions are shown in the official language in which they were submitted.
~8~
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-
;~!
~a~L9~
-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 ~
4 133-0583
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.
7 133-0583
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~
- 8 - 133-0583
- 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.
~31 9&~
-1O- 133-0583
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
EXAMPLE 2
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).
-11 133-0583
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).
-12- 133-0583
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).
EXAMPLE 8
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
-14- 133-0583
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).
10 EXAMPLE 9
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.
20 EXAMPLE 10
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.
-16 133-0583
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.
EXAMPLE 12
Following the procedure of Example 11, N-methoxy-N-methoxycarbonyl-
methyl-2-amino-5-(3-chloro-5-trifluoromethyl-2-pyridyloxy)aniline is
15 prepared.
EXAMPLE 13
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.
-17- 133-0583
13.4 N-methoxy-N-methoxycarbonylmethyl-2-chloro-5-(3-chloro-5-trifluoro-
methyl-2-pyridyloxy)aniline.
EXAMPLE 14
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.
-18- 133-0583
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 BL5after post-em application of less than 0.05 kg/ha against GR and
ofless than 0.07 kg/ha against BL.
133-0583
_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.
20- 133-0583
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.
-21- 133-0583
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.
