Note: Descriptions are shown in the official language in which they were submitted.
1236851
ACIDS AND ESTERS OF 5-(2-OPTIONALLY SUBSTITUTED-4-TRIFLUOROMETHYL-
6-OPTIONALLY SUBSTITUTED PIIENOXY)-2-NITRO, -HALO, OR -SWEENEY
ALPHA SUBSTITUTED PHENOL CARBONLESS, OXIDES AND
CAR BOXY OXIDES
BACKGROUND OF THE INVENTION
Field of the Invention
The invention pertains to compounds as defined by the graphic
Formula II, mentioned herein, their use to control weeds, and their
method of preparation. This application is a division of Applicant's
cop ending application Serial no. 351,078, filed May l, 1980.
Summary of the Invention
The invention of the aforementioned application concerns useful
compounds graphically represented by Formula I, mentioned herein, the
useful aldehydes, kittens, and oxides of the compounds graphically
represented by Formula II and Formula III, mentioned herein; the method
of preparing the compounds; and the method of controlling the weeds
described herein with the compounds. For example, 5-(2-chloro-4-trifluoro-
methylphenoxy)-2-nitroacetophenone oxime-O-(acetic acid, methyl ester) or
5-(2-chloro-4-trifluoromethylphenoxy)-2-chlorobenzzaldoxime-0-(2-propionic
acid, methyl ester) are useful for controlling weeds described herein.
The compounds represented by Formula III form the subject matter of a
separated divisional application.
~368~
DETAILED DESCRIPTION OF THE INVENTION
The novel, agriculturally useful compounds in both their
anti and sync forms are graphically represented by Formula I:
R Al (It
YO-YO C--N--O--C--C--O--R
3 O A 2 X H
z
wherein Y is hydrogen or chlorine; Z is chlorine when Y is chlorine, or Z is
hydrogen when Y is chlorine or hydrogen; X is vitro (-N02), a halogen,
preferably sheller (Of-), or cyan (-ON); R is hydrogen or an alkyd of up
to three carbon atoms, preferably methyl (-SHEA); Al is hydrogen or methyl
(-SHEA); and R2 is hydrogen, an alkyd of up to ten carbon atoms, preferably
an alkyd of up to four carbon atoms (methyl is especially preferred); or an
agronomlcally soluble salt ion, e.g. a metal ion such as sodium, potassium,
lithium, or ammonium (NH4 ), or a moo-, do-, or trialkyl substituted
ammonlum ion such as trimethylammonium or monoethanol ammonium ion; pro-
furred are sodium, potassium, and ammonium. -
Some examples of compounds of Formula I are:
I. R is an alkyd of up to three carbon atoms;
a. X is a halogen; and Y, Z, Al, and R2 are as defined.
ammonium5-(2-chloro-4-trifluoromethylphenoxy)-2-chloroproppiophenone oxide-
O-acetate,
20 5-(2-chloro-4-trifluoromethylphenoxy)-2-iodo-2'-meethylpropiophenone oxide-
0-(2- prop ionic acid, bottle ester),
5-(4-trlfluoromethylphenoxy)-2-fluorobutyrophenonee oxime-0-(2-propionic
acid, decal ester),
sodium5-(2,6-dichloro-4-trifluoromethylphenoxy)-2-bromoppropiophenone oxide-
O-acetate,
,..
~236851
5-(2,6-dichloro-4-trifluoromethylphenoxy)-2-chloroopropiophenone oxime-O-(2-
prop ionic acid, l,l-dimethyl ethyl ester),
5-(4-trifluoromethylphenoxy)-2-chloro-2-methylproppiophenone oxime-0-(acetic
acid, 3,4,5-dimethylheptyl ester).
b. Zeus cyan; and Y, Z, R , and R are as defined.
5-(4-trifluoromethylphenoxy~-2-cyanobutyrophenone oxime-0-(acetic acid,
hotly ester),
5-(2-chloro-4-trifluoromethylphenoxy)-2-cyanopropiiophenone oxime-O-(acetic
acid, nonyl ester),
sodium5-(2,6-dichloro-4-trifluoromethylphenoxy)-2-cyano--2-methylpropio-
phenone oxime-0-acetate,
5-(2-chloro-4-trifluoromethylphenoxy)-2-cyanoacetoophenone oxime-0-(2-pro-
picnic acid, ethyl ester),
5-(2-chloro-4-trifluoromethylphenoxy)-2-cyanobutyrrophenone oxime-O-(acetic
acid, 2-ethylhexyl ester).
c. X is vitro; and Y, I R , and R are as defined.
5-(2,6-dichloro-4-trifluoromethylphenoxy)-2-nitrobbutyrophenone oxime-O-
(2-propionic acid, propel ester),
5-(4-trifluoromethylphenoxy)-2-nitrobutyrophenone oxime-O-(2-propionic
acid, bottle ester),
methylammonium5-(2-chloro-4-trifluoromethylphenoxy)-2-nitro-2'-mmethyl-
propiophenone oxime-O-acetate,
5-(2,6-dichloro-4-trifluoromethylphenoxy)-2-nitrobbutyrophenone oxime-O-
(2-propionic acid, l,l-dimethylpropyl ester),
5-(2-chloro-4-trifluoromethylphenoxy)-2-nitropropiiophenone oxime-O-(acetic
acid, pentanyl ester),
I
~23685~L
5-(2-chloro-4-trifluoromethylphenoxy)-2-nitropropiiophenone oxime-0-(2-
prop ionic acid, decal ester),
5-(2,6-dichloro-4-trifluoromethylphenoxy)-2-nitroaacetophenone oxime-0-
(acetic acid, isobutyl ester),
5-(2-chloro-4-trifluoromethylphenoxy)-2-nitroacetoophenone oxime-0-(acetic
acid, isopropyl ester).
II. R is hydrogen;
a. X is a halogen: and Y, Z, R , and R2 are as defined.
dimethylammonium5-(2-chloro-4-trifluoromethylphenoxy)-2-chlorobenzzaldoxime-
0-acetate,
sodium5-(4-trifluoromethylphenoxy)-2-iodobenzaldoxime-0--acetate,
5-(2-chloro-4-trifluoromethylphenoxy)-2-fluorobenzzaldoxime-0-(2-propanoic
acid, 2,3,5-trlmethylheptyl),
5-(2-chloro-4-trifluoromethylphenoxy)-2-chlorobenzzaldoxime-0-(2-propanoic
acid, methyl ester),
5-(2,6-dichloro-4-trifluoromethylphenoxy)-2-bromobbenzaldoxime-0-(acetic
acid, bottle ester),
5-(4-trifluoromethylphenoxy)-2-fluorobenzaldoxime--Aztec acid, pentanyl
ester).
b. X it cyan: and Y, Z, R , and R2 are as defined.
5-(2-chloro-4-trifluoromethylphenoxy)-2-cyanobenzaaldoxime-0-(acetic acid,
2-methylpropyl ester),
5-(2-chloro-4-trifluoromethylphenoxy)-2-cyanobenzaaldoxime-0-acetic acid,
5-(2-chloro-4-trifluoromethylphenoxy)-2-cyanobenzaaldoxime-0-2-propionic
acid,
~236851.
5-(2-chloro-4-trifluoromethylphenoxy)-2-cyanobenzaaldoxime-0-(2-propionic
acid, l-methylethyl ester),
sodium5-(2-chloro-4-trifluoromethylphenoxy)-2-cyanobenzaaldoxime-0-(2-
preappoint),
5-(2,6-dichloro-4-trifluoromethylphenoxy)-2-cyanobbenzaldoxime-0-(acetic
acid, methyl ester),
trimethylammonium5-(4-trifluoromethylphenoxy)-2-cyanobenz~ldoxime-00-acetate,
5-(2-chloro-4-trifluoromethylphenoxy)-2-cyanobenzaaldoxime-0-(acetic acid,
3,5-dimethyloctyl ester),
ammonium5-(2,6-dichloro-4-trifluoromethylphenoxy)-2-cyanobbenzaldoxime-0-(2-
preappoint),
5-(4-trifluoromethylphenoxy)-2-cyanobenzaldoxime-00-acetic acid,
5-(2-chloro-4-trifluoromethylphenoxy)-2-cyanobenzaaldoxime-0-(2-propionic
acid, propel ester).
c. X is vitro; and Y, Z, Al, and R are as defined.
S-(4-trifluoromethylphenoxy)-2-nitrobenzaldoxime-0Aztec acid, 1,1-
dimethylethyl ester),
5-(2-chloro-4-trifluoromethylphenoxy)-2-nitrobenzaaldoxime-0-(2-propionic
acid),
5-(2,6-dichloro-4-trifluoromethylphenoxy)-2-nitrobbenzaldoxime-0-(2-propionic
acid, bottle ester),
5-(2-chloro-4-trifluoromethylphenoxy)-2-nitrobenzaaldoxime-0-(acetic acid,
bottle ester),
5-(2-chloro-4-trifluoromethylphenoxy)-2-nitrobenzaaldoxime-0-(2-propionic
acid, l,l-dimethylethyl ester),
5-(2-chloro-4-trifluoromethylphenoxy)-2-nitrobenzaaldoxime-0-(acetic acid,
nonyl ester),
I, . Jo
~23685~
5-(2,6-dichloro-4-trifluoromethylphenoxy)-2-nitrobbenzaldoxime-0-(acetic
acid, ethyl ester)
sodium5-(2-chloro-4-trifluoromethylphenoxy)-2-nitrobenzaaldoxime-0-acetate,
5-(2-chloro-4-trifluoromethylphenoxy)-2-nitrobenzaaldoxime-0-(acetic, acid,
2-methylnonyl ester),
triethylammonium5-(4-trifluoromethylphenoxy)-2-nitrobenzaldoxime-00-acetate,
5-(2-chloro-4-trifluoromethylphenoxy)-2-nitrobenzaaldoxime-0-(2-propionic
acid),
5-(4-trifluoromethylphenoxy)-2-nitrobenzaldoxime-00-(2-propionic acid, hotly
ester).
Novel compounds having useful herbicidal properties and utility
as intermediates in the formation of the compounds represented by Formula I
are:
A. Compounds Graphically Represented by Formula II
R (II)
CF3 X
wherein X, Y, Z, and R are as defined herein.
Some examples of general Formula II are:
5-(2-chloro-4-trifluoromethylphenoxy)-2-nitrobenzaalluded,
5-(4-trifluoromethylphenoxy)-2-nitrobenzaldehyde,
5-(2,o-dichloro-4-trifluoromethylphenoxy)-2-nitrobbenzaldehyde,
5-(2-chloro-4-trifluoromethylphenoxy)-2-nitroacetoophenone,
5-(2-chloro-4-trifluoromethylphenoxy)-2-nitropropiiophenone,
5-(4-trifluoromethylphenoxy)-2-nitroacetophenone,
.
1236851
5-(4-trifluoromethylphenoxy)-2-cyanobutyrophenone,,
5-(2-chloro-4-trifluoromethylphenoxy)-2-bromopropiiophenone,
5-(2,6-dichloro-4-trifluoromethylphenoxy)-2-fluorooacetophenone,
5-(4-trifluoromethylphenoxy)-2-nitro-2'-methylproppiophenone,
5-(2-chloro-4-trifluoromethylphenoxy)-2-chlorobenzzaldehyde,
5-(2-chloro-4-trifluoromethylphenoxy)-2-cyanobenzaalluded,
5-(4-trifluoromethylphenoxy)-2-chloropropiophenonee.
B. Compounds Graphically Represented by Formula III
R (III)
MY ,___" C--NOH
CF3 X
wherein X, Y, Z, and R are as defined herein:
Some examples of general Formula III are:
5-(2-chloro-4-trifluoromethylphenoxy)-2-nitrobenzaaldoxime,
5-(4-trifluoromethylphenoxy)-2-nitrobenzaldoxime,
5-(2,6-dichloro-4-trifluoromethylphenoxy)-2-nitrobbenzaldoxime,
5-(2-chloro-4-trifluoromethylphenoxy~-2-nitroacetoophenone oxide,
5-(4-trifluoromethylphenoxy)-2-nitroacetophenone oxide,
5-(2-chloro-4-trifluoromethylphenoxy)-2-nitrobutyrrophenone oxide,
5-(2,6-dichloro-4-trifluoromethylphenoxy)-2-nitroppropiophenone oxide,
5-(4-trifluoromethylphenoxy)-2-cyanobutyrophenone oxide,
5-(2,6-dichloro-4-trifluoromethylphenoxy)-2-nitro--2'-methylpropiophenone
oxide,
5-(2-chloro-4-trifluoromethyl-6-fluorophenoxy)-2-ffluorobenzaldoxime.
123~8~;1
As used herein and in the claims, the word "compound" and the
name of the compound, for example 5-(2-chloro-4-trifluorophenoxy)-2-nitro-
acetophenone oxime-O-(acetic acid, methyl ester) refers to sync and anti
isomers of the compound, as well as to other stereo isomers of the compounds.
Although all of the compounds as disclosed herein are useful for
the purposes disclosed herein, some compounds are preferred over others. In
the compounds described herein, Z is preferably hydrogen; X is preferably a
cyan, more preferably sheller (Of), but especially vitro (NO); Y is prey-
drably sheller (-Of); R is preferably hydrogen or methyl (SHEA); and R is
lo preferably an alkyd of up to four carbon atoms, especially methyl (SHEA)
or hydrogen, but also preferred are the agronomically useful salt ions men-
toned herein, particularly sodium (No+), potassium (K+), and ammonium (NH+4).
A very useful group of compounds graphically represented by For-
mute I and a very useful group of aldehydes, kittens, and oxides graphic
gaily represented by Formulas II and III are those of Formula IV, V, and VI:
R Irk 1 (IV)
Y C = N - O - C - C - O - R2
CF3 NO H
IT (V)
y COO
CF3 2
R (VI)
Y C = NO
CF3 NO
in which Y, Z, R9 Al, and R2 are as defined.
-- 8 --
, I , .,
1:~36851
A. Representative examples of these very useful compounds of
Formula IV are those in which:
I. R is an alkyd of up to three carbon atoms, and
a. Al is methyl such as:
5-(4-trifluoromethylphenoxy)-2-nitrobutyrophenone oxime-O-(2-propionic
acid, methyl ester),
5-(2-chloro-4-trifluoromethylphenoxy)-2-nitro-2'-mmethylpropiophenone
oxime-0-(2-propionic acid, bottle ester),
5-(2,6-dichloro-4-trifluoromethylphenoxy)-2-nitrobbutyrophenone oxime-O-(2-
prop ionic acid, l,l-dimethylethyl ester),
5-(4-trifluoromethylphenoxy)-2-nitropropiophenone oxime-0-(2-propionic
acid, l-methylpropyl ester),
5-(2-chloro-4-trifluoromethylphenoxy)-2-nitropropiiophenone oxime-(2-pro-
picnic acid, methyl ethyl ester),
5-(2,6-dichloro-4-trifluoromethylphenoxy)-2-nitroaacetophenone oxime-0-(2-
prop ionic acid, propel ester),
5-(2-chloro-4-trifluoromethylphenoxy)-2-nitroacetoophenone oxime-0-(2-pro-
picnic acid, ethyl ester),
5-(2,6-dichloro-4-trifluoromethylphenoxy)-2-nitroaacetophenone oxime-0-(2-
prop ionic acid).
b. Al is hydrogen, such as:
5-(2-chloro-4-trifluoromethylphenoxy)-2-nitro-2'-mmethylpropiophenone
oxime-0-(acetic acid, l,l-dimethyl ester),
5-(4-trifluoromethylphenoxy)-2-nitrobutyrophenone oxime-0-(acetic acid,
l-methylpropyl ester),
5-(2,6-dichloro-4-trifluoromethylphenoxy)-2-nitrobbutyrophenone oxime-O-
(acetic acid, 2-methylpropyl ester),
or .
sly
5-(2-chloro-4-trifluoromethylphenoxy)-2-nitropropiiophenone oxime-0-(acetic
acid, bottle ester),
5-(4-trifluoromethylphenoxy)-2-nitropropiophenone oxime-0-(acetic acid,
propel ester),
5-(2,6-dichloro-4-trifluoromethylphenoxy)-2-nitroaacetophenone oxime-0-(acetic
acid, methyl ethyl ester),
sheller- 4 trifluoromethylphenoxy-2-nitroacetophenone oxime-0-acetic acid,
5-(2,6-dichloro-4-trifluoromethylphenoxy)-2-nitro--2'-methylpropiophenone
oxime-0-acetic acid.
II. R is hydrogen and
a. Al is methyl such as:
5-(4-trifluoromethylphenoxy)-2-nitrobenzaldoxime-00-(2-propionic acid, 1,1-
dimethylethyl ester),
5-(2-chloro-4-trifluoromethylphenoxy)-2-nitrobenzaaldoxime-0-(2-propionic
acid, methyl ethyl ester),
5-(2,6-dichloro-4-trifluoromethylphenoxy)-2-nitrobbenzaldoxime-0-(2-propionic
acid, bottle ester),
5-(4-trifluoromethylphenoxy)-2-nitrobenzaldoxime-00-(2-propionic acid).
b. Al is hydrogen, such as:
5-(4-trifluoromethylphenoxy)-2-nitrobenzaldoxime-0Aztec acid, l,l-dimethyl-
ethyl ester),
5-(2-chloro-4-trifluoromethylphenoxy)-2-nitrobenzaaldoxime-0-(acetic acid,
2-methylpropyl ester),
5-(2,6-dichloro-4-trifluoromethylphenoxy)-2-nitrobbenzaldoxime-0-(acetic
acid, ethyl ester),
5-(2-chloro-4-trifluoromethylphenoxy)-2-nitrobenzaaldoxime-0-acetic acid.
-- 10 --
,, .
1236851
B. Examples of very useful kittens and aldehydes represented by
Formula V are those in which:
I. R is hydrogen, such as:
5-(2-chloro-4-trifluoromethylphenoxy)-2-nitrobenzaalluded,
5-(4-trifluoromethylphenoxy)-2-nitrobenzaldehyde,
5-(2,6-dichloro-4-trifluoromethylphenoxy)-2-nitrobbenzaldehyde.
II. R is an alkyd of up to three carbon atoms, such as:
5-(2-chloro-4-trifluoromethylphenoxy)-2-nitroacetoophenone,
5-(2-chloro-4-trifluoromethylphenoxy)-2-nitropropiiophenone,
5-(4-trifluoromethylphenoxy)-2-nitroacetophenone.
C. Examples of very useful oxides graphically represented by
Formula VI are those in which:
I. R is hydrogen. such as:
5-(2-chloro-4-trifluoromethylphenoxy)-2-nitrobenzaaldoxime,
5-(4-trifluoromethylphenox~y)-2-nitrobenzaldoxime,,
5-(2,6-dichloro-4-trifluoromethylphenoxy)-2-nitrobbenzaldoxime.
II. R is an alkyd of up to three carbon atoms, such as:
5-(2-chloro-4-trifluoromethylphenoxy)-2-nitroacetoophenone oxide,
5-(4-trlfluoromethylphenoxy)-2-nitroacetophenone oxide,
5-(2-chloro-4-trifluoromethylphenoxy)-2-nitrobutyrrophenone oxide,
5-(2,6-dichloro-4-trifluoromethylphenoxy)-2-nitroppropiophenone oxide.
Preferred compounds represented by Formula I are:
5-(2-chloro-4-trifluoromethylphenoxy)-2-nitroacetoophenone oxime-0-(acetic
acid, ethyl ester).
"I
'I '
1~36851
5-(2-chloro-4-trifluoromethylphenoxy)-2-nitroacetoophenone oxime-0-(2-pro-
picnic cold, methyl ester),
5-(2-chloro-4-trifluoromethylphenoxy)-2-nitroacetoophenone oxime-0-(2-
prop ionic said, ethyl ester),
5-(2-chloro-4-trifluoromethylphenoxy)-2-nitroacetoophenone oxime-0-(acetic
acid, methyl ester,
5-(2-chloro-4-trifluoromethylphenoxy)-2-nitrobenzaaldoxime-0-(acetic acid,
methyl ester),
5-(2-chloro-4-trifluoromethylphenoxy)-2-nitrobenzaaldoxime-0-acetic acid,
sodium5-(2-chloro-4-trifluoromethylphenoxy)-2-nitrobenzaaldoxime-0-acetate,
5-(2-chloro-4-trifluoromethylphenoxy)-2-nitroacetoophenone oxime-0-acetic
acid,
potassium5-(2-chloro-4-trifluoromethylphenoxy)-2-nitroacetoophenone oxide-
0-acetate,
5-(2-chloro-4-trifluoromethylphenoxy)-2-nitroacetoophenone oxime-0-(2-pro-
picnic acid).
The ammonium, sodium, and potassium salts of the above-mentioned
acetic and 2-propionic acids:
5-(2-chloro-4-trifluoromethylphenoxy)-2-chloroacettophenone oxime-0-(acetic .
acid, ethyl ester),
5-(2-chloro-4-trifluoromethylphenoxy)-2-chloroacettophenone oxime-0-(2-
prop ionic acid, methyl ester),
5-(2-chloro-4-trifluoromethylphenoxy)-2-chloroacettophenone oxime-0-(2-pro-
picnic acid, ethyl ester),
(2-chloro-4-trifluoromethylphenoxy)-2-chloroacetopphenone oxime-0-(acetic
acid, methyl ester),
5-(2-chloro-4-trifluoromethylphenoxy)-2-chlorobenzzaldoxime-0-(2-propionic
acid,
~L~3~8~1
5-(2-chloro-4-trifluoromethylphenoxy)-2-chlorobenzzaldoxime-0-acetic acid,
shellertrifluoromethylphenoxy)-2-chlorobenzaldoxime-0-(2--prop ionic
acid, methyl ester),
5-(2-chloro-4-trifluoromethylphenoxy)-2-chlorobenzzaldoxime-0-(acetic acid,
methyl ester).
The ammonium, sodium, and potassium salts of the above-mentioned
acetic and 2-propionic acids:
5-(2-ehloro-4-trifluoromethylphenoxy)-2-cyanoacetoophenone oxime-0-(acetic
acid, ethyl ester),
5-(2-chloro-4-trlfluoromethylphenoxy)-2-cyanoacetoophenone oxime-0-(2-
prop ionic acid, methyl ester),
5-(2-chloro-4-trifluoromethylphenoxy)-2-cyanoacetoophenore oxime-0-(2-
prop ionic acid, ethyl ester),
5-(2-chloro-4-trifluoromethylphenoxy)-2-cyanoacetoophenone oxime-0-(acetic
acid, methyl ester),
5-(2-ehloro-4-trifluoromethylphenoxy)-2-cyanobenzaaldoxime-0-(acetie acid,
methyl ester),
5-(2-chloro-4-trifluoromethylphenoxy)-2-cyanobenzaaldoxime-0-acetic acid,
sodium5-(2-chloro-4-trifluoromethylphenoxy)-2-cyanobenzaaldoxime-0-acetate,
5-(2-chloro-4-trifluoromethylphenoxy)-2-cyanoacetoophenone oxime-0-acetic-
acid,
potassium5-(2-chloro-4-trifluoromethylphenoxy)-2-cyanoacetoophenone oxide-
0-acetic acid,
5-(2-chloro-4-trifluoromethylphenoxy)-2-cyanoacetoophenone oxime-0-(2-pro-
pun acid).
Very preferred compounds in order of increasing preference are:
The sodium, potassium, and ammonium salts of:
I 1 .
~3685~
5-(2-chloro-4-trifluoromethylphenoxy)-2-cyanobenzaaldoxime-0-(2-propionic
and acetic acids),
5-(2-chloro-4-trifluoromethylphenoxy)-2-cyanoacetoophenone oxime-0-(2-pro-
picnic and acetic acids),
5-(2-chloro-4-trifluoromethylphenoxy)-2-chlorobenzzaldoxime-0-(2-propionic
and acetic acids),
5-(2-chloro-4-trifluoromethylphenoxy)-2-chloroacettophenone oxime-0-~2-pro-
picnic and acetic acids),
The compounds of:
5-(2-chloro-4-trifluoromethylphenoxy)-2-cyanobenzaaldoxime-0-(2-propionic-
acid),
5-(2-chloro-4-trifluoromethylphenoxy)-2-cyanobenzaaldoxime-0-acetic cold,
5-(2-chloro-4-trifluoromethylphenoxy)-2-cyanobenzaaldoxime-0-(2-propionlc,
methyl ester),
5-(2-chloro-4-trifluoromethylphenoxy)-2-cyanobenzaaldoxime-0-(acetic acid,
methyl ester),
5-(2-ehloro-4-trifluoromethylphenoxy)-2-cyanoacetoophenone oxime-0-(2-pro-
picnic acid),
5-(2-chloro-4-trifluoromethylphenoxy)-2-cyanoacetoophenone oxime-0-acetic acid,
5-(2-chloro-4-trifluoromethylphenoxy)-2-cyanoacetoophenone oxime-0-(2-pro-
pun acid, methyl ester),
5-(2-ehloro-4-trifluoromethylphenoxy)-2-cyanoacetoophenone oxime-0-(acetic
acid, methyl ester),
5-(2-chloro-4-trifluoromethylphenoxy)-2-chlorobenzzaldoxime-0-(2-propionic
acid),
5-(2-ehloro-4-trifluoromethylphenoxy)-2-chlorobenzzaldoxime-0-acetic acid,
5-(2-chloro-4-trifluoromethylphenoxy)-2-chlorobenzzaldoxime-0-(2-propionic
acid, methyl ester),
_ 14 -
3685~
5-(2-chloro-4-trifluoromethylphenoxy)-2-chlorobenzzaldoxime-0-(acetic acid,
methyl ester),
5-(2-chloro-4-trifluoromethylphenoxy)-2-chloroacettophenone oxime-0-(2-pro-
picnic acid),
5-(2-chloro-4-trifluoromethylphenoxy)-2-chloroacettophenone oxime-0-acetic
acid,
5-(2-chloro-4-trifluoromethylphenoxy)-2-chloroacettophenone oxime-O-(2-pro-
picnic, methyl ester),
5-(2-chloro-4-trifluoromethylphenoxy)-2-chloroacettophenone oxime-O-(acetic
acid, methyl ester),
5-(2-ehloro-4-trifluoromethylphenoxy)-2-nitrobenzaaldoxime-O-(2-propionic
and acetic acids),
5-(2-chloro-4-trifluoromethylphenoxy)-2-nitroacetoophenone oxime-O-(2-pro-
picnic and acetic acids),
5-(2-ehloro-4-trifluoromethylphenoxy)-2-nitrobenzaaldoxime-O-(2-propionic
acid),
5-(2-chloro-4-trifluoromethylphenoxy)-2-nitrobenzaaldoxime-O-acetic acid,
5-(2-ehloro-4-trifluoromethylphenoxy)-2-nitrobenzaaldoxime-0-(2-propionic
acid, methyl ester),
0 5-(2-chloro-4-trifluoromethylphenoxy)-2-nitrobenzaaldoxime-O-(acetic acid,
methyl ester).
5-(2-chloro-4-trifluoromethylphenoxy)-2-nitroacetoophenone oxime-O-(2-pro-
plan acid),
5-(2-ehloro-4-trifluoromethylphenoxy)-2-nitroacetoophenone oxime-O-acetic
acid,
5-(2-chloro-4-trifluoromethylphenoxy)-2-nitroacetoophenone oxime-O-(2-pro-
pionlc acid, methyl ester),
- 15 -
Jo .' ''
lX368Sl
5-(2-chloro-4-trifluoromethylphenoxy)-2-nitroacetoophenone oxime-0-(acetic
acid, methyl ester),
The most preferred compound is 5-(2-chloro-4-trifluoromethylphen-
oxy)-2-nitroacetophenone oxime-0-(acetic acid, methyl ester).
SYNTHESIS
A. General Procedure
Although the synthesis of the compounds described herein can be
performed by any of the procedures known to those skilled in the art, one
appropriate synthesis for the compounds described herein is described
herein and illustrated by the synthesis examples.
a. Formation of the Carboxv Compounds
1. Formation of the kitten and alluded compounds other than the
Sweeney substituted compounds
The appropriately substituted p-chlorobenzotrifluoride is reacted
with an appropriately substituted salt of a metal-3-substituted carbonyl
phenoxide or its petal or acutely or a cation of sodium (No+) or potassium
(K+), preferably K+, to form a compound of Formula II, where X is hydrogen,
which is then halogenated or nitrated by standard methods to form a come
pound of Formula II, which is separated from the reaction mixture.
2. Formation of the Sweeney substituted kitten and aldehvde compounds
The compounds of general Formula I (where X = cyan) may be pro-
pared by reduction of the carbonyl compound (or its acutely or petal) of
general Formula II (where X = vitro) to the amino compound (X = NH2) lot-
lowed by diazotizatlon and treatment with Quicken, affording the cyanocarbonyl
compound general Formula II where X = cyan). Subsequent conversion to
the oxide (Formula III where X = cyan) and car boxy oxides (Formula I where
X cyan) can be accomplished by methods described herein.
- 16 -
. . .
~2:~6851
b. Formation of Oxides
1. Procedure When R is Hydrogen
When R is hydrogen, the appropriate alluded represented by For-
mute II wherein R is hydrogen; for example (0.001 mole) is dissolved in
20 milliliters of tetrahydrofuran TO and 12 milliliters of absolute
ethanol. To this stirred solution is added hydroxylamine hydrochloride
(.012 mole) in 1 milliliter of water, and then .6 grams (.015 mole) sodium
hydroxide in 5 milliliters of water. The solution is stirred overnight at
ambient temperature and the tetrahydrofuran and ethanol are stripped off in
vacua, leaving a two-phase system. The oil phase is dissolved in sheller-
form (HCCL3) and then separated from the aqueous phase. The chloroform
layer is then extracted with water, and with a saturated sodium chloride
solution, and then dried over an hydrous magnesium sulfate (McCoy). Filter-
lion and evaporation affords the crude product of the oxides of Formula III
wherein R is hydrogen. The crude product can be recrystallized in carbon
tetrachloride (CC14).
2. Procedure When R is an Alkyd of up to Three Carbon Atoms
An alternate procedure is used when R in Formula II is an alkyd
described herein. This procedure employs an hydrous conditions. For exam-
pie (0.0056 mole) of the appropriate carbonyl compound of Formula If,
wherein R is an alkyd as defined herein, is dissolved in 20 milliliters of
a 1:1 mixture of absolute ethanol and dry Bunsen. To this solution is
added .77 grams of hydroxylamine hydrochloride in 15 milliliters of absolute
ethanol and 1.12 grams of any organic tertiary amine, such as triethylamine,
which is preferred. The solution is heated to reflex and the water formed
in the reaction is azeotroped off. After refluxing for 18 hours, the sol-
vent is removed in vacua, the residue is dissolved in chloroform, extracted
- 17 -
~23685~
Wylie water and saturated sodium chloride solution, and dried over an hydrous
magnesium sulfate. Filtration and evaporation affords the crude product
oxlmes of general Formula III where R is alkyd.
c. Procedure for Forming CarboxYlate
The appropriate oxide of general Formula III, prepared as above,
(0.004 mole) is dissolved in four milliliters of an alkanol of up to four
carbon atoms and is added to an alkoxide solution (0.0045 mole of sodium).
To this solution is added 0.0045 mole of the appropriate -halo-substituted
carboxylate compound where the halo is chlorine, bromide, or iodine, prey-
drably bromide, and the reaction is followed by thin layer chromatography The solution can be heated at reflex, if the reaction is sluggish. The
product of general Formula I is obtained either by filtration of the prod-
vat, or by evaporation of the solvent, and dissolving the residue in Shelley-
reform, extracting with water, drying and then evaporating the chloroform
solvent.
Sodium hydrides can be used in place of the sodium alkoxide, and
the solvent can be an ether such as tetrahydrofuran, or deathly ether, etc.
The compounds where R is hydrogen, such as 5-(2-chloro-4-tri-
fluoromethylphenoxy)-2-nitroacetophenone oxime-0-acetic acid, are prepared
by Rumple hydrolysis of the esters, followed by acidification and extract
lion or filtration of the product.
The compounds where R is an agronomically soluble salt, as defined
herein, are made by reacting the appropriate acid with the appropriate base.
b. Examples
The following examples illustrate the synthesis of compounds of
general Formula I by the general procedure described above.
- 18 -
So
EXAMPLE I
Synthesis of 5-(2-chloro-4-trifluoromethylphenoxy)-2-nitro-
acetophenone oxime-0-(acetic acid, methyl ester)
a. Preparation of 3-(2-chloro-4-trifluoromethylphenoxy)acetophenone
To a 250 milliliter flask containing a solution of 13.92 grams
of the potassium salt of 3-hydroxyacetophenone in 30 milliliters of dry
dimethylsulfoxide (DMSO), was added 17.12 grams (0.08 mole) of 3,4-dichloro-
benzotrifluoride. The reaction solution was heated to 175C. for six hours,
and then cooled and stirred at ambient temperature for 18 hours. The bulk
of the DMS0 was removed in vacua, and the remaining dark residue was stirred
with deathly ether for 15 minutes and filtered. The filtrate was extracted
once with water, once with lo sodium hydroxide, once with a saturated sodium
chloride solution, dried over an hydrous McCoy, filtered, decolonized with
charcoal, and evaporated to dryness leaving 16.04 grams of dark red oil come
prosed of 3-(2-chloro-4-trifluoromethylphenoxy) acetophenone. The material
was further purified by passing through a neutral, grade III alumina column.
b. Nitration of 3-(2~chloro-4-trifluoromethylpheno~y~acetophenone
To a 100 milliliter flask containing a solution of 26 milliliters
of concentrated sulfuric acid (H2S04), and 16 milliliters of ethylenedi-
chloride (ED), which was cooled to 0C., 6.28 grams, (0.02 mole) of the
dark red oil of3-(2-chloro-4-trifluoromethylphenox~J)acetophenonee (prepared
above) was added drops to form a brownish-black solution. When the add-
lion of 3-(2-chloro-4-trifluoromethylphenoxy)acetophenone was completed, dry
potassium nitrate (KN03), (2.0 grams, 0.020 mole) was added in small port
lions over a 20 minute period so as to maintain the reaction mixture below
4C. The reaction mixture was stirred for 0.5 hours at 0C. It was then
poured into 250 milliliters of ice and water, and the resulting mixture was
-- 19 --
I;
1~368~1
mixed with 200 milliliters of chloroform, (SCHICK). The organic layer
was separated, and then extracted twice with water, once with a saturated
sodium chloride solution, and then dried over an hydrous magnesium sulfate,
and then filtered. The organic solvent was evaporated off to yield 6.51
grams of an orange oil which analysis showed was a mixture of two post-
tonal isomers, one of which was 5-(2-chloro-4-trifluoromethylphenoxy)-2-
nitroacetophenone. The mixture was separated into two fractions by high
pressure liquid chromatography (HPLC) using deathly ether as the eluant.
The diethylether was stripped from fraction #1, leaving 2.37
grams of an orange oil comprised of 5-(2-chloro-4-trifluoromethylphenoxy)-2-
nitroacetophenone which had the following:
Nuclear magnetic resonance [(NOR) (GDC13)]:
2.47~ (singlet, OH); 6.78-8.21~ (multiple, OH).
Infer Red (IT): 1710, 1575, 1520, 1400, 1315 cm
Mass Spectra (MS) molecular ion at m/e 359.
c. Synthesis of 5-(2-chloro-4-trifluoromethyl-
phenoxy)-2-nitroacetophenone oxide
A 100 milliliter flask was charged with a solution of 2.0 grams
(0.0056 mole) of the orange oil, 5-(2-chloro-4-trifluoromethylphenoxy)-2-
nitroacetophenone, in 10 milliliters of absolute ethanol and 10 molehill-
lens of dry Bunsen. A solution of hydroxylamine hydrochloride (0.77 grams,
0.011 mole) in 15 milliliters of absolute ethanol was added followed by
addition of 1.12 grams ~0.011 mole) of an acid acceptor (triethylamine).
The reaction mixture was then reflexed; when 20 milliliters of solvent was
distilled off, an additional 15 milliliters of Bunsen was added. Refluxing
was continued until 15 milliliters of solvent distilled off, and then the
remaining solution was reflexed for 16 hours, with the formation of a mixture
- 20 -
lZ36851
of the sync and anti isomers of 5-(2-chloro-4-trifluoromethylphenoxy)-2-
nitroacetophenone oxide. The solvent was stripped from the mixture, and
the residue was dissolved in chloroform. The chloroform solution was
extracted twice with water, then with a saturated solution of sodium
chloride, and then dried over an hydrous magnesium sulfate.
The chloroform solution was filtered and the solvent (sheller-
form) was evaporated to yield 2.03 grams of an orange oil comprised of
5-(2-chloro-4-trifluoromethylphenoxy)-2-nitroacetoophenone oxide (anti and
sync), which had the following:
Mass spectra (MS): molecular ion at m/e 374
(Sync and Anti) NOR (CDC13): 2.13~ (singlet, OH),
OWE (multiple, OH); 9.33~ (singlet, lo).
(Sync and Anti) IRK 3100 (broad), 1605, 1575, 1520, 1400 cm 1.
d. Formation of the Sync and Anti Isomers of sheller-
4-trifluoromethylphenoxy)-2-nitroacetophenone
oxime-0-(acetic acid, methyl ester)
A solution of 0.10 grams (0.0045 milliliters) of sodium metal in
5 milliliters of methanol under nitrogen was charged into a 25 milliliter
flask. When all of the sodium had reacted, 1.50 grams (0.004 mole) of
the5-(2-chloro-4-trifluoromethylphenoxy)-2-nitroacetoophenone oxide (anti
and sync (prepared above) dissolved in 5 milliliters of methanol was added,
and the solution stirred. Methylbromoacetate (0.68 grams, 0.0045 mole)
was added to the solution; the resulting mixture was stirred at ambient
temperature under nitrogen for eighteen (18) hours, and was then reflexed
for two hours. The solvent was stripped from the solution and the residue
was dissolved in chloroform (SCHICK). The SCHICK solution was extracted
twice with water, once with a saturated sodium chloride solution, and dried
- 21 -
, I.
1;Z ~685~
over an hydrous magnesium sulfate. The SCHICK solution was filtered, and the
solvent removed by evaporation to yield 1.68 grams of an orange oil contain-
in the isomers of5-t2-chloro-4-trifluorome~hylphenoxY~-2-nitroacetoophenone
oxime-O-(acetic acid, methyl ester). The orange oil was purified by cry-
matography by dissolving it into 3 milliliters of ethyl ether and placing it
on top of a seven inch by 21 millimeter column of grade III alumina. The
column was eluded with deathly ether and the desired fractions were collected.
The solvent was removed to yield 0.72 grams of a yellow oil comprised of anti
and sync isomers of5-(2-chloro-4-trifluoromethylphenoxy)-2-nitroacetoophenone
lo oxlme-O-(acetic acid, methyl ester), which had the following:
MS: molecular ion at m/e 446
Sync and Anti IRK 1760, 1605, 1575, 1520, 1320 cm
yo-yo and Anti NOR (CDC13): 2.23S (singlet, OH),
3.67S and 3.72~ (singlet, OH), 4.47S and 4.67
(singlet, OH), 6.78-8.25 (multiple, OH).
Upon dissolving the yellow oil in ethanol (or methanol), pale
yellow crystals were obtained with a melting point of 89-92C.
EXAMPLE II
Synthesis of the Anti and Sync Isomers of sheller-
4-trifluoromethylphenoxy)-2-nitroacetophenone oxide-
Acetic acid, ethyl ester)
A solution of 0.14 grams (0.0060 mole) of sodium metal in 8 Millie
liters of methanol under nitrogen gas was charged into a 50 milliliter
flask. When all us the sodium had reacted, 2.0 grams (0.0053 mole) of the
orange oil, anti and sync isomers of 5-(2-chloro-4-trifluoromethylphenoxy)-
2-nitroacetophenone oxide (prepared as in Example Icy were added, and the
solution was stirred. Ethyl-2-bromopropionate (loo grams, 0.0059 mole)
- 22
3685~
were added to the solution and resulting mixture was stirred at ambient
temperature under nitrogen gas for fifty-one (51) hours. The solvent was
stripped from the solution, and the oil residue was stirred in deathly
ether, filtered, and washed well with deathly ether. The filtrate was
washed twice with water, once with a saturated sodium chloride solution,
and dried over an hydrous magnesium sulfate. The deathly ether solution was
then filtered, and the solvent removed by evaporation to yield 2.23 grams
of an orange oil containing the anti and sync isomers of 5-(2-chloro-4-tri-
fluoromethylphenoxy)-2-nitroacetophenone oxime-O-(acetic acid, ethyl ester).
The orange oil was purified by chromatography by dissolving it in deathly-
ether and adding it to the top of an eight inch by 21 millimeter column of
neutral grade III alumina. The column was eluded with diethylether and the
first component to come off the column was the desired product. The sol-
vent way removed to yield 1.13 grams of a yellow oil comprised of anti and
sync isomers of5-(2-chloro-4-trifluoromethylphenoxy)-2-nitroacetoophenone
oxlme-O-(acetic acid, ethyl ester).
EXAMPLE III
Synthesis of 5-(2-chloro-4-trlfluoromethylphenoxy)-2-
chlorobenzaldoxime-O-(acetic acid, methyl ester)
a. Preparation of 3-(2-chloro-4-trifluoromethylphenoxy)-
benzaldehyde dim ethyl acutely
To a solution of 80.7 grams (0.39 mole) of the potassium (K+) salt
of 3-hydroxybenzaldehyde dim ethyl acutely in 170 milliliters of dry DMSO was
added 77.04 grams (0.36 mole) of 3,4-dichlorobenzotrifluoride. The soul-
lion was heated in an oil bath of 150-155~ for four hours and then stirred
overnight at ambient temperature.
- 23 -
~2~6851
The solvent was then stripped in vacua and the residue stirred
with SCHICK and filtered. The filtrate was washed with HO, 0.5 N Noah and
saturated awl solution and dried over an hydrous McCoy. Filtration and
decolonization with charcoal and evaporation of solvent afforded 114.8 grams
of a light orange oil comprised of 3-(2-chloro-4-trifluoromethylphenoxy)-
benzaldehyde dim ethyl aretal.
b. Preparation of 5-(2-chloro-4-trifluoromethyl
phenoxy)-2-chlorobenzaldehyde
A 200 milliliter (ml) three-necked flask was charged with ten
(10.0) grams (0.029 mole) of the above-mentioned 3-(2-chloro-4-trifluoro-
methylphenoxy)benzaldehyde dim ethyl acutely and 90 milliliters of dry
ethylene dichlorides The solution was cooled in an ice bath, and then a
catalytic amount (approximately 0.2 grams) of ferris chloride was added to
the solution. Chlorine gas addition was started at a moderate rate and
continued for one (1) hour at 0C., and then the solution was stirred for
an additional two (2) hours at 0C. The reaction solution was then purged
with nitrogen overnight at ambient temperature.
It was then extracted with water (HO) and the HO layer extracted
with chloroform (SCHICK). The organic layers of ethylene dichlorides and
chloroform were combined and again washed with H20 (the HO being brought to
pi 6 with lo Noah). The organic layer was then washed with saturated Nail
solution and dried over an hydrous McCoy. Filtration and evaporation afforded
11.74 grams of a pale yellow oil comprised of 5-(2-chloro-4-trifluoromethyl-
phenoxy)-2-chlorobenzaldehyde, which had the following NOR, IRK and MS:
NOR: (CDC13) 6.87-7.600~ (multiple, OH) 10.37~ (singlet, lo).
IRK 1695, 1605, 1590, 1500, 1415, 1320 cm
MS: Molecular ion at m/e 334.
123685~
c. Preparation of 5-(2-chloro-4-trifluoromethyl-
phenoxy)-2-chlorobenzaldoxime
A 100 milliliter flask was charged with 3.34 grams (.01 mole)
of the prepared5-(2-chloro-4--trifluoromethylphenoxy)-2-chlorobennzaldehyde,
20 milliliters of tetrahydrofuron (THY) and 12 milliliters of absolute
ethanol. To this solution was added 0.83 grams (.012 mole) of hydroxyl-
amine hydrochloride in ten (10) milliliters of water, and then 0.60 grams
(.015 mole) of Noah in five (5) milliliters of H20. After stirring the
solution at ambient temperature for approximately eighteen (18) hours, the
solution was stripped (I vacua) of the organic solvent and the aqueous
residue taken up in a mixture of H20/CHC13. The organic layer was phase
separated, washed with saturated Nail solution and dried over an hydrous McCoy.
Filtration and evaporation afforded 3.01 grams of a beige solid.
This material was recrystallized in 40 milliliters of hexane, affording
1.24 grams of beige crystals comprised of 5-(2-chloro-4-trifluoromethyl-
phenoxy)-2-chlorobenzaldoxime (anti and sync which had an mop. of 109-112C.
and the following NOR and IRK
NOR: (CDC13) 6.83-7.70~ (multiple, OH), 8.45 (singlet, lo),
~.97~ (singlet, lo).
IRK 3340-3110, 1605, 1590, 1570, 1485, 1400, 1320 cm
d. Preparation of 5-(2-chloro-4-trifluoromethylphenoxy)-
2-chlorobenzaldoxime-0-(acetic acid, methyl ester)
A 25 milliliter flask was flushed with dry nitrogen (No) and then
charged with .09 grams (.0037 mole) of sodium and 5 milliliters of dry moth-
anon. When all of the sodium had reacted, 1.24 grams (.00355 mole) of the
5-(2-chloro-4-trifluoromethylphenoxy)-2-chlorobenzzaldoxime in 4 milliliters
of methanol was added. After stirring for 15 minutes, 0.57 grams (.0037
mole) of methyl bromoacetate was added and the solution was stirred over-
night (under dry nitrogen) at ambient temperature.
I I''.
Jo
~3~i~351
Solvent was then removed in vacua, the residue dissolved in SCHICK,
and extracted with water and saturated Nail solution and dried over ashy-
dross McCoy. Filtration and evaporation of the solvent afforded 1.53 grams
of a pale yellow oil. This was dissolved in 2 milliliters of SCHICK and
added to the top of a silica gel-60 column (35 gram, 70-230 mesh, activity
2-3) and eluded with SCHICK. The eluant was collected in 10 milliliter free-
lions and analyzed by thin layer chromatography (TLC). Evaporation of the
appropriate fractions (of the first component off the column) afforded 1.02
grams of a clear, colorless oil comprised of 5-(2-chloro-4-trifluoromethyl-
phenoxy)-2-chlorobenzaldoxime-0-(acetic acid, methyl ester), which had the
following:
NOR: (CDC13) 3.75 (singlet, OH); 4.71~ (singlet, OH);
multiple centered at 7.31~ (OH);
8.56~ (singlet, lo).
IRK 1760, 1740, 1595, 1565, 1500, 1465, 1320 cm
MS: Molecular ion at m/e 421.
EXAMPLE IV
Synthesis of 5-(2-chloro-4-trifluoromethylphenoxy)-2-
chlorobenzaldoxime-O-(2-proPionic acid, methyl ester)
A 25 milliliter flask was flushed with dry nitrogen (No) and
charged with 6 milliliters of dry Mesh and .15 grams (.0065 mole) of sodium.
When all of the sodium had reacted, 2.09 grams (.006 mole) of the 5-(2-
chloro-4-trifluoromethylphenoxy)-2-chlorobenzaldoxtime (prepared as in Exam-
pie I a.) in 6 milliliters of Mesh was added in one portion and stirred
for approximately fifteen (15) minutes at ambient temperature.
To this solution was added 1.12 grams (.0062 mole) of ethyl-2-
bromoprcpionate in one portion. The resulting solution was stirred at
ambient temperature under dry nitrogen overnight.
- 26 -
f
1;~36851
Solvent was then stripped and the residue dissolved in SCHICK,
phase separated and the SCHICK layer extracted with saturated Nail solution
and dried over an hydrous McCoy. Filtration and evaporation of solvent left
3.0 grams of a crude oil. This was dissolved in 2 milliliters of SCHICK and
applied to the top of a silica gel-60 column (wet-packed with SCHICK) (40 gram,
70-230 mesh, activity 2-3) and eluded with SCHICK. The eluant was collected
in 10 milliliter fractions and analyzed by thin layer chromatography (TLC).
Evaporation of the appropriate fractions (fractions 6-13) afforded 1.94 grams
of q clear, colorless oil comprised of 5-(2-chloro-4-trilfluoromethylphenoxy)-
2-chlorobenzaldoxime-0-(2-propionic acid, methyl ester), which had the
following:
NOR (CDC13): 1.46 (doublet, OH); OWE (singlet, OH);
4.73 (quartet, lo); 7.188 (multiple, OH);
8.44 (singlet, lo);
IRK 1760, 1610, 1600, 1565, 1500, 1465, 1320 cm ; and
MS: Molecular ion at m/e 435.
The following compounds were prepared by procedures described
herein and illustrated by Examples I, II, III, and IV.
EXAMPLE V
5-(2-chloro-4-trifluoromethylphenoxy)-2-nitroacetoophenone oxide-
0-(2-propionic acid, methyl ester), a yellow oil which had the following:
NOR (CDC13): 1.29S and 1.51~ (2 doublets, OH);
OWE (singlet, OH);
3.69~ and 3.73~ (2 singlets, OH);
4.64~ and 4.80~ (2 quartets, lo);
7.0 - OWE (multiples, OH).
IRK 1760, 1575, 1525, 1315 cm ; and
MS: Molecular ion at m/e 460.
- 27 -
~Z3685~
EXAMPLE VI
5-(2-chloro-4-trifluoromethylphenoxy)-2-nitroacetoophenone oxide-
O-acetic acid, a yellow oil prepared by saponification of methyl ester,
which had the following:
NOR (CDC13): 2.19 (singlet, OH);
owe and 4.71~ (singlets, OH);
6.93 - 8.24 (multiple, OH);
10.92 (singlet, lo); and
IRK 3000-3400 (broad), 1730, 1575, 1525, 1315 cm
EXAMPLE VII
5-(2-chloro-4-trifluoromethylphenoxy)-2-nitrobenzaaldoxime, a
viscous semi-solid with the following:
NOR (CDC13): 6.93 - 8.136 (multiple, OH);
8.13~ (singlet, lo);
9.49~ (broad singlet, lo);
IRK 3310 (broad), 1605, 1570, 1520, 1490, 1400, 1315 cm 1; and
MS: Molecular ion at m/e 360.
EXAMPLE VIII
5-(2-chloro-4-trifluoromethylphenoxy)-2-nitrobenzaaldoxime-0-
(acetic cold, methyl ester), when recrystallized from Mesh, gave a pale
yellow solid (mop. 72-76) which had the following:
NOR (CDC13): 3.76 (singlet, OH); 4.72 (singlet, OH);
6.93 - 7.79~ (multiple, OH);
8.13~ (doublet, lo); 8.78~ (singlet, lo);
IRK 1755, 1600, 1565, 1515, 1315 cm ; and
MS: Molecular ion at m/e 432.
- 28 -
Jo :
sly
EXAMPLE IX
5-(2-chloro-4-trifluoromethylphenoxy)-2-nitrobenzaaldoxime-0-(2-
prop ionic acid, methyl ester), a pale yellow liquid with the following:
NOR (CDC13): 1.52~ (doublet, OH); 3.72~ (singlet, OH);
4.84~ (quartet, lo);
multiple centered at 7.35~ (OH),
8.125 (doublet, lo), 8.758 (singlet, lo);
IRK 1750, 1605, 1565, 1520, 1315 cm
MS: Molecular ion at m/e 446.
EXAMPLE X
5-(2-chloro-4-trifluoromethylphenoxy)-2-nitrobenzaaldoxime-0-
(acetic acid, isopropyl ester), a yellow crystalline solid with the lot-
lowing:
NOR (CDC13): 1.23~ (doublet, OH); 4.638 (singlet, OH);
5.06~ (septet, lo);
multiple centered at 7.33~ (OH);
8.09~ (doublet, lo), 8.63~ (singlet, lo);
IRK 2980, 2940, 1750, 1605, 1570, 1520, 1315 cm ; and
MS: Molecular ion at m/e 460.
Applications of the Compositions Against Weeds
The novel compounds of this invention are particularly valuable
for reemergence and pot emergence weed control because they are toxic to
many species and groups of weeds and are relatively nontoxic to many bone-
filial plants. The exact amount required of one or more of the compounds
described herein depends upon a variety of factors, including the hardiness
- 29 -
''''.
I';
236851
of the particular weed species, the weather, the type of soil, the method
of application, the kind of beneficial plants in the same area, and the
like. Thus, while the application of up to only about 0.1 pounds of active
compound per acre may be sufficient for good control of a light infestation
of weeds growing under adverse conditions, the application of 2 pounds or
more of an active compound per acre may be required for good control of a
dense infestation of hardy perennial weeds growing under favorable condo-
lions. The preferred compounds mentioned herein are generally used at the
lower application rates such as from 0.1 to 10 pounds per acre; the less
preferred but generally useful compounds are generally applied at the
higher applications of from 10 to 20 pounds per acre, and those compounds
which are intermediate between the most preferred compounds and the gent
orally useful compounds are generally applied at rates from 5 to 15 pounds
per acre.
a. Examples of Weeds Which May Be Controlled
by the Compounds Described Herein
Weeds are undesirable plants growing where they are not wanted
and may be classified as broadleaf or grassy weeds, a classification which
includes many types of known weeds. Many weeds are controlled by the
compositions set forth herein, when applied in a herbicidally effective
amount. These include:
Aster sup., e.g.
Aster spinosus Berth. (aster, spiny)
Aster simplex Will. (aster, white field)
Aster parry Gray (aster, woody)
Hordeum leporinum Link (barley, wild)
- 30 -
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~236851
Gallium 5pp ., e.g.
Gallium apron L. (bed straw, couched)
Gallium asprellum Michx. (bed straw, rough)
Gallium v sum L. (bed straw, yellow)
Sundown dactyl on (L.) Pens. (Bermuda grass)
Convolvulus arvensis L. (bindweeds, field)
Convolvulus septum L. (bindweeds, hedge)
Fagopyrum tataricum (L.) Gaertn. (buckwheat, Tartary)
Syrup 8pp ., e.g.
Syrups atrovirens Will. (bulrush, green)
Scripts fluviatilis (Torn.) Gray (bulrush, river)
Arctium 8Pp ., e.g.
Arctium minus (Hill) Berth. (burdock, common)
Mollugo verticillata L. (carpeted)
Caucus karat L. (carrot, wild)
Silent Shari Baumg. (champion, biennial)
Silent cucubalus Libel (champion, bladder)
Luckiness floscuculi L. (champion, meadow)
Luckiness Dick L. (champion, red)
Tough sup., e.g.
Tough latifolia L. (cattail, common)
Anthems sup., e.g.
Anthems arvensis L. (chamomile, corn)
Brahms sup., e.g.
Bruce cyclones L. (cheat)
Brahms tectorum L. (downy broke)
-
- 31 -
Jo .
~Z~368~;1
Styler media (L.) Cyril (chickweed, common)
Cerastium sup., e.g.
Cerastium vul~atum L. (chickweed, Moser)
A~rostemma ~itha~o L. (cockle, corn)
Saponaria vaccaria L. (cockle, cow)
Luckiness alga Mill. (cockle, white)
Crouton sup., e.g.
Crouton ~ladulosus L. (crouton, tropic)
Quaff Petiolata (L.) Cohesion (quaff, clammy)
Quaff cartha~enensis (Jack.) McBride (quaff, towered)
Taraxacum spy e.g.
Taraxacum officinale Weber (dandelion, common)
Remix 8PP., e.g.
Remix crisps L. (dock, curly)
Remix assets L. (sorrel)
Cuscuta 8PP., e.g.
Cuscuta indecora Choosy (dodder, large seed)
Cuscuta planiflora Tenure (dodder, small seed)
Eupatorium capillifolium (Lam.) (dog fennel)
Heteranthera limos (So.) Will. (duck salad)
Roy vir~inica (L.) Will. (dwarf dandelion, Virginia)
Emex Australia Stein. (emex)
Emex spoons Camp. (emex, spiny)
Pyrrhopappus Carolinians (Walt.) DO (false dandelion, Carolina)
Fumier officinalis L. (fumitory)
Eleusine indict (L.) Gaertn. (goose grass)
Lithospermum sup., e.g.
Lithospermum officinale L. (Cromwell, common)
- 32 -
;~?' I.
sly
Synch sup ., e.g.
Synch volleyers L. (groundswell, common)
Galeopsis titrate L. (hemp nettle)
Selenium sup ., e.g.
Selenium Carolinians L. (horizontal)
Equisetum sup ., e.g.
Enuisetum arvense L. (hairstyle, field)
CYno~los3um officinale L. (hounds tongue)
Vernonia sup ., e.g.
Vernonia altissima Null. (ironed, tall)
Sinatra sup., e.g.
Sinatra ripens L. (nipped, Russian)
Sinatra maculosa Lam. (nipped, spotted)
Scleranthus annuls L. (Noel)
olygonum, sup., e.g.
Polygonum aviculare L. (nutted, prostrate)
Polv~onum convolvulus L. (buckwheat, wild)
Polonium PensYlvanicum L. (smarted, Pennsylvania
Couch scoParla (L.) Squired. (couch)
Muddle Carolinian (L.) G. Don (mallow, bristly)
Malta sup., e.g.
Malta neRlecta Wall. (mallow, common)
Hibiscus trionum L. (mallow, Venice)
Medicare lupulina L. (medic, black)
Panicum obtusum H.B.K. (mesquite, vine)
Asclepias sup , e.g.
Asclepias circa L. (milkweed, common)
Asclepias verticillata L. (milkweed, western whirled)
- 33 -
sly
Sarcostemma cYanchoides Dane. (milkweed, climbing)
Ampelamus albidus (Null.) Bitt. (milkweed, honey vine)
Verbs scum sup ., e.g.
Verbascum thaPsus L. (Mullen, common)
Nazi sup ., e.g.
Nazi marina L. (naiad, holly leaf)
Cyprus stargazes L. (nut sedge, false)
Cyprus rotundas L. (nut sedge, purple)
Cvperus esculentus L. (nut sedge, yellow)
Panicum sup ., e.g.
Panicum dichotomiflorum Michx. (panicum, fall
Panicum taxonomy Buckle (panicum, Texas)
Thlaspi arvense L. (pancreas, field)
Thlaspi Perfoliatum L. (pancreas, thoroughwort)
PotamoReton sup., e.g.
Potamogeton nodosus Pour. (pounded, American)
Portulaca oilers L. (porcelain, common)
Required scabra L. . (porcelain, Florida)
ARropyron ripens (L.) Beau. (quack grass)
Ambrosia sup ., e.g.
Ambrosia artemisiifolia L. (ragweed, common)
Ambrosia trifida L. (ragweed, giant)
Ambrosia PsilostachYa DO (ragweed, western)
Echinochloa colonum (L.) Link (~ungle-rice)
O'er saliva L. (rice, red)
Lolium multiflorum Lam. (rigors, Italian)
- 34 -
, . . .
~LZ36851
Sesbania vesicaria (Jack.) Eli. (sesbania, bag pod)
Sesbania exaltata (Ray.) Cony (sesbania, hemp)
Couch obtusifolia L. (cyclopedia)
Leptochloa uninervia (press) Hitch. &
Chase (sprangletop, Mexican)
Leptochloa filiformis (Lam.) Beau. (sprangletop, red)
Euphoria sup., e.g.
Euphoria cYParissias L. (spurge, cypress)
Euphoria supine Raft (spurge, prostrate)
Euphoria maculate L. (spurge, spotted)
Panicum vir~atum L. (switch grass)
Spryly arvensis L. (slurry, corn)
Cnicus Benedict us L. (thistle, blessed)
Echium volleyer L. (thistle, blue)
Cirsium spy e.g.
Cirsium volleyer (Save) Tenure (thistle, bull)
Cirsium arvense (L.) Scope (thistle, Canada)
arrowheads nuttiness L. (thistle, musk)
Soullessly kale L. var. tuneful Bausch (thistle, Russian)
Lunar sup., e.g.
Lunar volleyers Hill (toad flax, yellow)
H~drochloa caroliniensis Beau. (water grass, southern)
Barbara vernal (mill.) Archers (winter cress, early)
Panicum capillary L. (witch grass)
Achilles millefolium L. (yarrows, common)
Achilles lanulosa Null. (yarrows, western)
- 35 -
~36851
The compounds of the invention, particularly the preferred come
pounds, for example,5-(2-chloro-4-trifluoromethylphenoxY)-2-chlorobenzbald-
oxime-O-(2-propionic acid, methyl ester), when applied post emergence at
rates as low as one (1) pound per acre (1.1 kilograms per Hector) or less
are very effective against weeds of the genera: Side, Dotter, Brusque,
Satyr, Sorghum, Sesbania, Abutilon, Ipomoea, Arena, and Echinochloa.
The compounds of the invention, particularly the preferred come
pounds, for example,5-(2-chloro-4-trifluoromethylphenoxy)-2-chlorobenzbald-
oxime-0-(2-propionic acid, methyl ester), when applied post emergence at
rates as low as one (1) pound per acre (1.1 kilograms per Hector) are very
effective against the weed species: Side spoons (L) (seaweed, Dotter
stramonium (L) (~imsonweed), Brasslca Faber DO (wild mustard), Satyr
glauca (L) (yellow foxtail), Digit aria sanguinalis (L) (large crabgrass),
Sorghum halepen~e (L) (~ohnsongrass), Sesbania sup. (Lo (coughed),
Abutllon theoPhrastl (L) (velvet leaf), IPomoea PurPurea (L) Roth (tall
morning glory), Arena fish (L) (wild oats), Echinochloa crusgalli (L)
(barnyard grass), and Gossypium hirsutum (L) (cotton as a weed).
The compounds of the invention, particularly the preferred come
pounds, for example,5-(2-chloro-4-trifluoromethylphenoxy)-2-chlorobenzbald-
oxime-0-(2-propionic, methyl ester), are safe to crops of corn, wheat,
and rice, when applied post emergence at rates of one (1) pound per acre
(1.1 kilograms per Hector) or less. Others are also safe to soybeans.
The compounds of the invention, particularly the preferred
compounds, for example, 5-(2-chloro-4-trifluoromethylphenoxy)-2-nitro-
acetophenone oxime-O-acetic acid, when applied reemergence at rates as
low as one-half (0.5) pound per acre (0.55 kilograms per Hector) are very
effective against weeds of the genera: Side, Dotter, Brusque, Satyr,
Digit aria, Sorghum, Sesbania, Abutilon, Ipomoea, Arena, and Echinochloa.
. "
3~851
The compounds of the invention, particularly the preferred come
pounds, for example,5-(2-chloro-4-trifluoromethylphenoxy)-2-nitroacetoo-
phenone oxime-O-acetic acid, when applied reemergence at rates as low
as one-half (0.5) pounds per acre (0.55 kilograms per Hector) are very
effective against the weed species: Side spoons (L) (seaweed), Dotter
strammonium (L) (jimsonweed), Brusque Faber DO (wild mustard), Satyr
Laura (L) (yellow foxtail), Dotter san~uinalis (L) (large crabgrass),
Sorghum halepense (L) (~ohnsongrass), Sesbania sup. (L) (coughed),
Abutilon theophrasti (1) (velvet leaf), Ipomoea purPurea (L) Roth (tall
mornlngglory), Arena fish (L) (wild oats, Echlnochloa crusgalli (L)
(barnyard brass), and Gossyplum hirsutum (L) (cotton as a weed).
The compounds of the invention, particularly the preferred come
pounds, for example5-(2-chloro-4-trlfluoromethylphenoxy)-2-nitroacetoo-
phenone oxlme-O-acetlc cold, are safe to crops of cotton, corn, and soy-
beans when applied reemergence at rates of one-half (0.5) pounds per
acre (0.5 kilograms per Hector). Other compounds as described herein are
safe on wheat and rice, as well as corn and cotton.
b. Description Of The Method Of Controlling Weeds
As used herein and in the claims, the method of controlling the
weeds comprises contacting the weeds with a herbicidally effective amount
of a composition represented by Formula I described herein. The term
"contacting the weeds" refers to any method of contacting the weeds, both
reemergence (before the weeds appear) and/or post emergence (after the
weeds appear), such as applying granules of the compound to the soil prior
to emergence, or spraying a solution of the compound or compounds described
by the general formula, or any other method known in the art by which the
:- "I
1236~51
weeds are contacted either before they emerge or after they emerge, or both
before and after they emerge, but preferably after they emerge with one
or more of the compounds represented by Formula I described herein. The
phrase "the herbicidally effective amount" refers to that amount required
under the environmental conditions in order to effectively control, that
is, the weeds are severely injured so as not to be able to recover from
the application of the compound or are killed. The phrase "a safe amount"
refers to that amount under environmental conditions which cause no sub-
staunchly injury to the crops.
c. Other Uses
The compounds of the invention may also be used as a discount,
defoliant, doesn't, or growth regulant, for examples, potato vine dozily-
cant, cotton defoliant as well as doesn't, or as a growth regulant for
brush growth control.
d. General Application Of The Compounds
For practical use as herbicides or other pesticidal use, the come
pounds of this invention are generally incorporated into herbicidal and/or
pesticidal formulations which comprise an "inert carrier and herbs-
dally and/or pesticidally toxic amount of one or more of the compounds
mentioned herein". Such formulations enable the active compound to be
applied conveniently to the appropriate site in any desired quantity.
These formulations can be solids such as dusts, granules, or wettable
powders or they can be liquids such as solutions, aerosols, or emulsifiable
concentrates.
12368~1
For example, dusts can be prepared by grinding and blending
the active compound with a solid inert carrier such as the talcs, clays,
silicas, pyrophyllite, and the like. Granular formulations can be prepared
by impregnating the compound, usually dissolved in a suitable solvent, onto
and into granulated carriers such as the attapulgites or the vermiculites,
usually of a particle size range of from about 0.3 to 1.5 millimeters.
Wettable powders, which can be dispersed in water or oil to any desired
concentration of the active compound, can be prepared by incorporating
wetting agents into concentrated dust compositions.
In some cases the active compounds are sufficiently soluble in
common organic solvents such as kerosene or zillion so that they can be
used directly as solutions in these solvents. Frequently, solutions of
herbicides can be dispersed under super atmospheric pressure as aerosols.
However, preferred liquid herblcidal formulations are emulsifiable con-
cent rates, which comprise an active compound according to this invention
and as the inert carrier, a solvent and an emulsifier. Such emulslfla-
bye concentrates can be extended with water and/or oil to any desired
concentration of active compound for application as sprays to the site of
the weed infestation. The emulsifiers most commonly used in these con-
cent rates are non ionic or mixtures of nonionlc with anionic surface-
active agents. With the use of some emulsifier systems, an inverted Emil-
soon (water in oil) can be prepared for direct application to weed infest
stations.
A typical herbicidal formulation according to this invention is
illustrated by the following example, in which the quantities are in
parts by weight.
- 39 -
.. :
`~: ,`, ,`
icily
EXAMPLE XI
PREPARATION OF A DUST
Product of Example I 10
Powdered Talc 90
The above ingredients are mixed in a mechanical grinder-blender
and are ground until a homogeneous, free flowing dust of the desired part-
ale size is obtained. This dust is suitable for direct application to the
site of the weed infestation.
d. Use Of Compounds Alone Or In Mixtures
Although all of the compounds described herein and represented
by Formula I described herein are useful as herbicides, some of these are
preferred and are better for applications against weeds. In general, all
ox the compounds described herein may be used either alone or together in
mixtures of the compounds described herein. When used in mixtures, the
amount or ratio of one compound to another may vary from 0.01 to 100. The
amount to use ranges from 0.10 pounds per acre to 2 pounds or more per acre
depending upon the conditions.
e. wanner Of Application Of The Compounds
Of This Invention
The compounds of this invention can be applied as herbicides in
any manner recognized by the art. One method for the control of weeds
comprises contacting the locus of said weeds with a herbicidal formulation
comprised of an inert carrier and one or more of the compounds of this
invention as an essential active ingredient, in a quantity which it herb-
tidally toxic to said weeds. The concentration of the new compounds of
- 40 -
lZ368S~
this invention in the herbicidal formulations will vary greatly with the
type of formulation and the purpose for which it is designed; but generally
the herbicidal formulations will comprise from about 0.05 to about 95 per-
cent by weight of the active compounds of this invention. In a preferred
embodiment of this invention, the herbicidal formulations will comprise
from about 5 to 75 percent by weight of the active compound. The formula-
lions can also comprise other pesticides, such as insecticides, nematocides,
fungicides, and the like; stabilizers, spreaders, deactivators, adhesives,
stickers, fertilizers, activators, synergisms, and the like.
The compounds of the present invention are also useful when come
brined with other herbicides and/or defoliants, desiccants, growth inhibit
ions, and the like in the herbicidal formulations heretofore described.
These other materials can comprise from about 5 percent to about 95 percent
of the active ingredients in the herbicidal compositions. Use of comber-
lions of the present invention provide herbicidal formulations which are
more effective in controlling weeds and often provide results unattainable
with separate formulations of the individual herbicides.
f. Examples Of Other Pesticides And
Herbicides For Combinations
The other herbicides, defoliants, desiccants, and plant growth
inhibitors, with which the compounds of this invention can be used in the
herblcidal formulations to control weeds, can include: chlorophenoxy
herbicides such as 2,4-D, 2,4,5-T,MCPA, MCPB, 4-(2,4-DB), 2,4-DEB, 4-CPB,
4-CPA, 4-CPP, 2,4,6-TB, TESS, 3,4-DA, silver and the like; carbamate
herbicides such as IPC, CIPC, swept bourbon, BCPC, CEPC, CPPC, and the like;
thiocarbamate and dithiocarbamate herbicides such as CDEC, metal sodium,
685~L
EPIC, dwelt, PUBIC, peculate, vernolate and the like; substituted urea
herbicides such as Norma, siduron, dichloroal urea, chloroxuron, cycluron,
fenuron, monuron, monuron TEA, Doreen, linuron, monolinuron, neuron,
bittern, trimeturon, and the like; symmetrical treason herbicides such as
Samson, chlorazine, desmetryne, norazine, ipazine, prometryn, atrazine,
trietazine, semitone, prometone, propazine, ametryne, and the like; sheller-
acetamide herbicides such as alpha-chloro-N,N-dimethylacetamide, IDEA,
CUD M , alpha-chloro-N-isopropylacetamide, 2-chloro-N-isopropylacetanilide,
4-(chloroacetyl)morpholine, l-(chloroacetyl)piperidine, and the like;
chlorinated aliphatic acid herbicides such as TEA, dalapon, 2,3-dichloro-
prop ionic acid, 2,2,3-TPA, and the like; chlorinated benzoic acid and
phenylacetic acid herbicides such as 2,3,6-TBA, 2,3,5,6-TBA, dicamba,
tricamba, amibien, fence, PEA, 2-methoxy-3,5-dichlorophenylacetic acid,
3-methoxy-2,6-dlchlorophenylacetic cold, 2-methoxy-3,5,6-trichlorophenyl-
acetic acid, 2,5-dichloro-3-nitrobenzoic acid, dual, metribuzin and the
like; and such compounds as aminotriazole, malelc hydrazide, phenol men-
curia acetate, endothall, Burt, technical chlordane, dim ethyl 2,3,5,6-
tetrachloroterephthalate, Dakota, erbon, DNC, DNBP, dichlobenil, SPA,
diphenamid, dipropalin, trifluralin, solar, dicryl, Morpheus, DMPA, DSMA,
MAMA, potassium aside, acrolein, benefit, Ben sulfide, AS, bromacil, 2-
t3,4-dichlorophenyl)-4-methyl-1,2,4-oxadiazolidineeden, bromoxynil,
cacodylic acid, COMA, CPMF, cypromid, DUB, DCPA, dichlone, dipheratril,
DMTT, SNAP, END, ioxynil, isocil, potassium Senate, MA, MAMA, MOPES,
MCPP, MY, molinate, NAP, parquet, POP, picloram, SPA, PICA, pyrichlor,
Suzanne, terbacil, terbutol, TUBA, LASS, planavin, sodium tetraborate, eel-
alum cyanamide, DEFY ethyl xanthogen disulfide, sundown, sundown B, pro-
panic and the like. Such herbicides can also be used with the compositions
- 42 -
or,
~3685~.
of this invention in the form of their salts, esters, asides, and other
derivatives whenever applicable to the particular parent compounds.
g. Examples of Herbicidal Control
The following examples illustrate the utility of the compounds
described herein, for the control of weeds.
The tests described herein were conducted in a laboratory under
laboratory conditions in accordance with standard herbicidal testing prove-
dunes for reemergence and post emergence control. The plants are observed
for a period of days after treatment, and observations were recorded to
determine if the weeds are controlled, that is severely injured so that the
plants do not recover, or are killed.
EXAMPLE XII
When5-(2-chloro-4-trifluoromethylphenoxy)-2-nitroacetoophenone
oxime-0-(acetic acid, methyl ester) from Example I was applied preener-
genre at two (2) pounds per acre to the weeds of Side spoons (L) (seaweed),
Dotter stramonium (L) (jimsonweed), Brusque Faber (L) (wild mustard),
Satyr glauca (L) (yellow foxtail), Digit aria san~uinalis (Lo (large
crabgrass), Sorghum halepense (L) (~ohnsongrass), Sesbania sup. (coffee-
weed), Abutilon theophrasti (L) (velvet leaf), IPomea purpurea (L) R _
(tall morning glory), Echinochloa crusgalli (L) barnyard grass all of the
weeds were controlled.
EXAMPLE XIII
When5-(2-chloro-4-trifluoromethylphenoxy)-2-nitroacetoophenone
oxime-0-(acetic acid, methyl ester) from Example I was applied post emergence
- 43 -
', '.'~
en
~36851
at two (2) pounds per acre to Side spoons (L) (seaweed); Dotter stramonium
(jimsonweed), Brusque Faber (wild mustard), Satyr glauca (L) (yellow)
foxtail, Gossypium hirsutum (cotton), Sesbania sup. (coughed), Abutilon
theoPhrasti (velvet leaf), Ipomoea purpurea (L) Roth (tall morning glory),
Sorghum halepense (Johnson grass), Arena fish (L) (wild oats), and Echino-
Shelley crossly (L) (barnyard grass), all the weeds were controlled within
21 days.
EXAMPLE XIV
When the compound 5-(2-chloro-4-trifluoromethylphenoxy)-2-
chlorobenzaldoxime-0-(acetic acid, methyl ester) from Example III was
applied reemergence at ten (10) pounds per acre (11.1 kilograms per
Hector) against the weeds: Side spoons (L) (seaweed), Dotter stramonium
(L) (jimsonweed), Brusque Faber DO (mustard, wild), Satyr glauca
(L) (yellow foxtail), Dotter sanRuinalis (Lo (large crabgrass), Sorghum
halepense (L) (~ohnsongrass), Sesbania sup. (L) (coughed), Abutilon
theoPhrasti (L) (velvet leaf), IPomoea purpurea (L) Roth (tall morning glory),
and Echinochloa crossly (L) (barnyard grass), all of the weeds were
severely injured and many were killed after twenty-three (23) days.
EXAMPLE XV
When the compound 5-(2-chloro-4-trifluoromethylphenoxy)-2-
chlorobenzaldoxime-0-(acetic acid, methyl ester) from Example III was
applied post emergence at one (1) pound per acre (1.1 kilograms per Hector)
against the weeds: Side spleens (L) (seaweed), Dotter stramonium (L)
(~imsonweed), Brasslca Faber DO (mustard, wild), Satyr glauca (L)
(yellow foxtail), Sorghum halepense (L) (Johnson grass), Sesbania sup. (L)
1~3685~
(coughed), Abutilon theophrasti (L) (velvet leaf), IPomoea purpurea (L)
Roth (tall morning glory), and GossYpium hirsutum (L) (cotton, as a weed),
all of the weeds were severely injured and many were killed after twenty-
two (22) days.
EXAMPLE XVI
When the compound 5-(2-chloro-4-trifluoromethylphenoxy)-2-chloro-
benzaldoxime-0-(2~propionic, methyl ester) from Example IV was applied
reemergence at four (4) pounds per acre (4.4 kilograms per Hector)
against the weeds: Side spoons (L) (seaweed), Dotter stramonium (L)
(jimsonweed), Brusque Faber DO (mustard, wild), Satyr Rlauca (L)
(yellow foxtail), Digit aria sanguinalis (L) (large crabgrass), Sesbania
eye (L) (coughed), Abutilon theophrasti (L) (velvet leaf), and IPomoea
PurPurea (L) Roth (tall morning glory), all of the weeds were severely
injured and many were killed after twenty-two (22) days, and it was safe
for corn, wheat, and rice.
EXAMPLE XVII
When the compound 5-(2-chloro-4-trifluoromethylphenoxy)-2-
chlorobenzaldoxime-0-(2-propionic, methyl ester) from Example IV was
applied post emergence at one (1) pound per acre (1.1 kilograms per Hector)
against the weeds: Side spoons (L) (seaweed), Dotter stramonium (L)
(~imsonweed), Satyr Rlauca (L) (yellow foxtail), Sorghum halePense (L)
(~ohnsongrass), Sesbania sup. (L) (coughed), Abutilon theoPhrasti (L)
(velvet leaf), Ipomoea purpurea (L) Roth (tall morning glory), Arena fish
(L) (wild oats), Echinochloa crusgalli (L) (barnyard grass), and Gossypium
hirsutum (L) (cotton, as a weed), all of the weeds were severely injured
:'. .,`~; :
36851
and many were killed after twenty-two (22) days, and it was safe for corn,
wheat, and rice.
EXAMPLE XVIII
When the compound 5-(2-chloro-4-trifluoromethylphenoxy)-2 vitro-
acetophenone-0-(2-propionic acid, methyl ester) from Example V was applied
reemergence at two (2) pounds per acre (2.2 kilograms per Hector) against
the weeds: Side spoons (L) (eddy, Dotter stramonium (L) (jimsonweed),
Brusque Faber DO (mustard, wild), Satyr glauca (L) (yellow foxtail),
Digit aria sanguinalis (L) (large crabgrass), Sorghum halepense (L) (John-
son grass), Sesbania sup. (L) (coughed), Abutilon theoPhrasti (L) (Yet-
vet leaf), Ipomoea purpurea (L) Roth (tall morning glory), Arena fish (L)
(wild oats), and Echinochloa crusgalli (L) (barnyard grass), all of the
weeds were severely injured and many were killed after 20 days.
EXAMPLE XIX
When the compound 5-(2-chloro-4-trifluoromethylphenoxy)-2-nitro-
acetophenone-0-(2-propionic acid, methyl ester) from Example V was applied
post emergence at two (2) pounds per acre (2.2 kilograms per Hector)
against the weeds: Side spoons (L) (seaweed), Dotter stramonium (L)
(Jimsonweed), Brusque Faber DO (mustard, wild), Satyr glauca (L)
(yellow foxtail), Sorghum halePense (L) (~ohnsongrass), Sesbania sup. (L)
(coughed), Abutilon theophrasti (L) (velvet leaf), Ipomoea purpurea (L)
Roth (tall morning glory), Arena fish (L) (wild oats), and Gossypium
hirsutum (L) (cotton, as a weed), all of the weeds were severely injured
and many were killed after twenty (20) days.
- 46 -
sly
EXAMPLE XX
When the compound 5-(2-chloro-4-trifluoromethylphenoxy)-2-nitro-
acetophenone-0-acetic acid from Example VI was applied reemergence at one-
half (0.5) pounds per acre (0.55 kilograms per Hector against the weeds:
Side spoons (L) (seaweed), Dotter stramonium (L) (jimsonweed), Brusque
Faber DO (mustard, wild), Satyr glauca (L) (yellow foxtail), Digit aria
sanguinalis (L) (large crabgrass), Sorghum halepense (L) (Johnson grass),
Sesbania sup . (L) (coughed), Abutilon theophrasti (L) (velvet leaf),
Ipomoea purpurea (L) Roth (tall morning glory), Arena future (L) (wild oats),
and Echinochloa crusgalli (L) (barnyard grass), all of the weeds were
s verily injured and many were killed after twenty-one (21) days, and it
was safe for cotton, soybeans, and corn.
EXAMPLE XXI
When the compound 5-(2-chloro-4-trifluoromethylphenoxy)-2-nitro-
acetophenone-0-acetic acid from Example VI was applied post emergence at
one-half (0.5) pounds per acre (0.55 kilograms per Hector) against the
weeds: Side spoons (L) (seaweed), Dotter stramonium (L) (~imsonweed),
Brusque Faber DO (mustard, wild), Satyr glauca (L) (yellow foxtail),
Sesbanla sup. (L) (coughed), Abutilon theophrasti (L) (velvet leaf),
Ipomoea purpurea (L) Roth (tall morning glory), and Gossypium hirsutum AL)
(cotton, as a weed), all of the weeds were severely injured and many were
killed.
EXAMPLE XXII
When the compound 5-(2-chloro-4-trifluoromethylphenoxy)-2-nitro-
benzaldoxime-0-(acetic acid, methyl ester) from Example VIII was applied
1~36851
reemergence at two (2) pounds per acre (2.2 kilograms per Hector) against
the weeds: Side spoons (Lo (seaweed), Dotter stramonium (L) (jimsonweed),
Brusque Faber DO (mustard, wild), Satyr glauca (L) (yellow foxtail),
Digit aria sanguinalis (L) (large crabgrass), Sesbania sup. (L) (coy food),
Abutilon theophrasti (L) (velvet leaf), and Ipomoea purpurea (Lo Roth (tall
morning glory), all of toe weeds were severely injured and many were killed
after twenty-one (21) days, and it was safe on soybeans, corn, and rice.
EXAMPLE XXIII
When the compound 5-(2-chloro-4-trifluoromethylphenoxy)-2-nitro-
lo benzaldoxime-0-(acetic acid, methyl ester) from Example VIII was applied
post emergence at one (1) pound per acre (1.1 kilograms per Hector) against
the weeds: Side spoons (L) (seaweed), Dotter stramonium (1) (jimsonweed),
Brusque Faber DO (mustard, wild), Sorghum halepense (L) (Johnson-
grass), Sesbania sup. (L) (coughed), Abutilon theophrasti (L) (velvet-
leaf), Ipomoea purPurea (L) Roth (tall morning glory), Echinochloa crusgalli
(L) (barnyard grass), and Gossypium hirsutum (L) (cotton, as a weed), all of
the weeds were severely injured and many were killed after twenty-seven
(27) days, and it was safe for soybeans and rice.
EXAMPLE XXIV
When the compound 5-(2-chloro-4-trifluoromethylphenoxy)-2-nitro-
benzaldoxime-0-(2-propionic acid, methyl ester) from Example IX was applied
reemergence at two (2) pounds per acre (2.2 kilograms per Hector) against
the weeds: Side spoons (L) (seaweed), Dotter stramonium (L) (jimsonweed),
Brusque Faber DO (mustard, wild), Satyr glauca (L) (yellow foxtail),
Digit aria sanguinalis (L) (large crabgrass), Sesbania sup. (L) (coughed),
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~:~36851
Abutilon theophrasti (L) velvet lea and Ipomoea purpurea (L) Roth (tall
morning glory), all of the weeds were severely injured and many were killed
after twenty-one (21) days, and many were killed after twenty-one (21)
days, and it was safe for corn and rice.
EXAMPLE XXV
When the compound 5-(2-chloro-4-trifluoromethylphenoxy)-2-nitro-
benzaldoxime-0-(2-propionic acid, methyl ester) from Example IX was
applied post emergence at one-half (0.5) pounds per acre (0.55 kilograms
per Hector) against the weeds: Side spoons (L) (seaweed), Dotter sire-
minim (L) (~imsonweed), Brusque Faber DO (mustard, wild), Sesbania
sup. (L) (coughed), Abutilon theoPhrasti (L) (velvet leaf), Ipomoea
purpurea (L) Roth (tall morning glory), and GossYPium hirsutum (L) (cotton,
as a weed), all of the weeds were severely injured and many were killed
after twenty-two (22) days, and it was safe for wheat and rice.
EXAMPLE XXVI
When the compound 5-(2-chloro-4-trifluoromethylphenoxy)-2-nitro-
ben~aldoxime-0-(acetic acid, isopropyl ester) from Example X was applied
reemergence at two (2) pounds per acre (2.2 kilograms per Hector) against
the weeds: Side spoons (L) (seaweed), Dotter stramonium (L) (~imsonweed),
Brusque Faber DO (mustard, wild), Satyr Luke (L) (yellow foxtail),
Digit aria sanguinalis (L) (large crabgrass), Sesbania sup. (L) (coughed),
Abutilon theophrasti (L) (velvet leaf), and IPomoea purpurea (L) Roth (tall
morning glory), all of the weeds were severely injured and many were killed
after twenty-two (22) days.
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: `', Jo
. ,
~;~36851
EXAMPLE XXVII
When the compound 5-(2-chloro-4-trifluoromethylphenoxy)-2-nitro-
benzaldoxime-0-(acetic acid, isopropyl ester) from Example X was applied
post emergence at two (2) pounds per acre (2.2 kilograms per Hector)
against the weeds: Side spoons (L) (seaweed), Dotter stramonium (L)
(jimsonweed), Brusque Faber DO (mustard, wild), _
(L) (large crabgrass), Sesbania sup. (L) (coughed), Abutilon theophrasti
(L) (velvet leaf), and Ipomoea purpurea (L) Roth (tall, morning glory), all
of the weeds were severely injured and many were killed after twenty-two
(22) days.
While the invention has been described with reference to specific
details of certain illustrative embodiments, it is not intended that it
shall be limited thereby except insofar as such details appear in the
accompanying claims.
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