Note: Descriptions are shown in the official language in which they were submitted.
~89~7~i
PR-5495
--1--
HALOACETAMIDINES AND THE HEREICIDAL
USE THEREOF
-
This invention relates to cert:ain novel halo-
acetamidines which are useful as herbicides. More
specifically, this invention relates to a novel herbicidal
compound known as acetamidines, more particularly
dichloroacetamidinesO
Back ound of the Invention
gr
Use o~ Herbicide_
An herbicide is a compound which controls or
modifies plant growth, e.g., killing, retarding, defoliating,
desiccating, regulating, stunting, tillering, stimulating,
and dwarfing. "Plant" refers to all physical parts,
including seeds, seedlings, saplings, roots, tubers, stems,
stalks, ~oliage, and fruits. "Plant growth" is meant to
include all phases of development from seed germination to
natural or induced cessation o~ life.
1~ ~erbicides are generally used to control or
eradicate weed pes~s. They ha~e gained a high degree of
commercial success because it has been shown tha~ such
control increases crop yield and reduces harvesting cos~s.
Herbicidal effectiveness is dependent upon
several ~ariables. ~ne of these is the ~ime or growth
related method of application. The most popular methods of
application include: pre-plan~ incorporation into the soil;
pre-emergence surface treatment o~ seeded soil; and post-
emergence treatment of the plant and soil.
The most importan~ determinant o~ herbicidal
effectiveness is ~he suscep~ibility of the target weed.
Certain herbicidal compounds are phyts~oxic to some weed
species but not to others.
The manufac~urer of the herbicide recommends a
range of rates and conc~ntrations calculated to maximize
, ~
8~
--2--
weed control. The range of rates varies from approximately
0.01 ~o 50 pounds per acre, usually from 0.1 to 2~ pounds
per acre. The actual amount used depends upon several
considerations including particular weed susceptibility and
overall cost limitations.
Prior Art
U.S. Patent 3,153,670 relates primarioy to vinyl
amines. A utility disclosed ~or the vinyl amines is the
prepara~ion of a~idines from primary amines. In U.S.
3,153,670 the following specific compo~lds are disclosed:
N,N-diethyl-N'-phenyl 2,2-dichloroacetamidine, N,N-diethyl-
N'-tolyl 2,2-dichloroacetamidine, N,N-diethyl-N'-p-chloro-
phenyl 2,2-dichloroacetamidine, N,N-diethyl-N'-p-nitro-
phenyl 2,2-dichloroacetamidine, and N,N-diethyl-N'-p--ethoxy-
phenyl 2,2-dichloroacetamidine. U.S. 3,153,670 generically
discloses herbicidal utility for the above compounds. No
specific testing or method of testing for herbi
activity is set forth in the cited patent.
The J. Am. Chem. Soc. 82 902-9 (1960) discloses
the compound N,N-diethyl-N'-phenyl 2,2-dichloroacetamidine.
U.S. Patent 3,576,618 discloses certain N-
trichloroacetamidines having the formula
~ C-CC13
Rn
These compounds are useful as herbicides. The form taken by
the compounds are the aryl amino form, thereby allowing only
one substituent on the aryl amino nitrogen and always a
hydrogen on the amino nitrogen with the phenyl moiety. These
are commonly known as "reverse" acetamidines.
Similarly, West German Of~enlegungschrift
2557651 rela~es ~o N-aryl-2,2-dihalo-acetamidine derivatives
of the general formula
8~
--3--
R ~ N-C~NH
H-C-X
R X
wherein Rl, R~ and R3 are the same or dif~erent and are
defined as a hydrogen, halogen atom, aliphatic moiety or
R4-o- wherein R4 is aliphatic or aromatic moiety and X is a
halogen a~om. These acetamidines are termed "reverse"
acPtamidines because of the tau~omeric system within the
molecule. The utility is disclosed as fungicidal.
The following are a group of patents which relate
to acetamidines in which the two (2) position is substituted
with a non-halogenated methyl group: U.S. 3,284,289, U S.
3,487,156, U.S. 3,781,356, U.S. 3,781,357, U.S. 3,803,134
and U.S. 3,867,448.
The compounds disclosed in the above-cited U.S.
patents are taught to be useful for the control of acarids
and insects, combating undesired plant growth, harmful
micro-organisms, nematodes.
U.S. Patent 3,428,681 relates to N-halotrichloro-
acetamidines having ~he general formula
- N C--NX
~ ~ CC13
wherein X is chlorine, iodine or bromine and each R is
independently selected from the group consis.ing of hydrogen,
alkyl, aryl, cycloalkyl and heterocyclic. These compounds
are disclosed as useful as bleaches and disinfectan~s,
effecti~e as fungicidal, herbicidal and algaecidal agents.
It is recognized the amidine compounds hav~ the
potential of existing in two geometrical isomeric forms,
known as tautomers, in the aryl mino form ~ArN=C(NHR ] and
~he aryl amino iorm [ArNHC(=NR)R ]. Many compounds contain-
ing an "amidine moiety" possess potential for tautomerism~
geometricaL isomerism and conformational change. The
s
--4--
"amidine moiety" refers to comyounds containing the poten-
tially tautomeric system -NH-C(X)--N- in which X is C, N, 0
or S as described by Jackman, L. M. et al., J. Am. Chem.
S _ 97 (10) 2811~18. In the present application the
predominant tautomer is presumed to be in the imino ~orm and
the representation of ~he dichloro acetamidines will be in
this form.
Description of the Inv~ntion
The compounds comprising the instan~ class o
compounds corresponds to the general formula
~R
Y N
~ N-C R2
X ~ A-CM
B
in which A and B are independently selec~ed ~rom the group
conslsting of hydrogen, 1uorine, chlorine, bromlne and
methyl, provided that at least one of A or B is other than
hydroge~;
X is selected from the group consist;ng of trifluoromethyl,
lower alkyl, nitro7 chloro, bromo, fluoro, cyano, lower
alkoxy acetyl, lower alkylthio, trifluoromethylthio, and
3,3-diloweralkyl ureido,
Y is selected from ~h~ group consisting of hydrogen, lower
alkyl, chloro, 1uoro, nitro, trifluoromethyl, and lower
alkoxy;
Z is selected from the group conslsting of hydrogen and
chloro;
Rl is selected from the group consisting o~ hyd~ogen; alkyl
and allyl;
R2 ls selected from the group consisting of alkyl, allyl7
ben~yl, hydroxyalkyl, alkynylj N alkyl amido, alkoxyalkyl,
dialkoxyalkyl, alkoxy~ cyano alkyl, substituted phenyl
7 S
--5--
wherein the substituent is selected from the group tri-
fluoromethyl, dichloro and 3,3-dimethylureido; and
Rl and R2 taken together with the nitrogen is selected from
the group consisting of alkyl substituted oxazolidyl and
alkyl substituted ~hiazolidyl, morpholinyl, piperidinyl and
pyrrolidinyl; and salts thereof
More particularly, with re~erence to the general
formula above: A, B and M are as defined and
X is selected from the group consisting of trifluoromethyl,
lower alkyl having 1 to 3 carbon atoms, inclusive, nitro,
chloro, bromog fluoroj cyano, lower alkoxy having 1 ~o 3
carbon atoms, inclusive, acetyl, lower alkylthio having 1
to 3 carbon atoms, inclusive, trifluoromethylthio and
3,3-diloweralkyl ureido in which each lower alkyl has from
1 to 2 carbon atoms, inclusive;
Y is selected ~rom the group consisting of hydrogen, lower
alkyl having 1 to 3 carbon a~oms, inclusive, chloro,
1uoro, nitro, trifluoromethyl and lower alkoxy having 1 to
3 ca~bon ato~s, inclusive;
Z is selected from the group consis~ing of hydrogen and
chloro;
Rl is selected from the group consistLng of hydrogen,
alkyl having 1 to 6 carbcn atoms, inclus~ve, and allyl;
~2 is selected from the group consisting of alkyl having
1 to 6 carbon atoms, inclusive, allyl, benzyl, hydroxy-
ethyl, alkynyl having 3 to 4 carbon atoms, inclusive,
N-alk~lamido in which the alkyl has 1 to 3 carbon atoms,
inclusive~ alkoxyalkyl having 2 to 6 carb~n atoms, in-
clusive, dialkoxyalkyl having 3 to 6 carbon atoms,
inclusive, alkoxy having 1 to 4 carbon atoms, inclusive,
cyanoalkyl having 2 ~o 4 carbon atoms, inclusive,
substitu~ed phenyl wherein said substituent is selected
from the group trifluoromethyl, dichloro and 3,3-
dimethylureidoy and
Rl and R2 taken together with the nitrogen is selected
fr~m the group consisting of alkyl substituted oxazolidyl
and alkyl substituted thiazolidyl wherein said oxazolidyl
~L~!39(~75
-6-
or thiazolidyl is substituted 1, 2 or 3 times wi~h alkyl
having from 1 to 3 carbon atoms, inclusive~ morpholinyl,
piperidinyl and pyrrolidinyl; and
salts thereof with an acid selected from the group consist-
ing of HCl, HBr, HI, HF, H2S04, CC13COOH, 2,4-dichlQro-
phenoxy ace~ic acid, 3-amino-2,5 dichlorobenzoic acid,
hexanoic acid, stearic acid, naphthalene acetic acid,
piYalic acid, succinic acid, 10-undecenoic acid, benzoic
acid, maleic acid and malonic acid.
The terms "lower alkyl" and "alkyll' includes
straight chain and branched chain substituents of this
type; the term "lower alkoxy" includes straight chain and
branched chain substituents of this type; the term
"alkynyl" includes substituent~ of this type having
straight or branched chain and at least one triple bond;
the terms "alkoxy alkyl" and "dialkyloxy alkyl" include
substituents o this type ha~ing a straight or branched
chain configuration; and cyanoalkyl includes substituents
having at least one cyano group (CN) and alkyl ln straight
or branched chain.
The compounds of this invention have been ~ound
to be ac~ive herbicides; that is, the compounds ha~e been
found to be herbicidally active against various species of
weeds. In the broadest sense, the term "weeds" refers to
plants which grow in locations in which they are not
desired. As will be seen from the data which follows,
these compounds show various activi~ies as pre-emergence
and/or post-emergence herbicides. In some cases they have
been found to show particular activity against certain weed
species.
This in~ention, therefore, also relates to a
method of controlling undesirable vegetation comprising
applying to such vegetation or the locus where sueh
vegetation is found, a herbicidall~ effective amount of a
compound as described herein, and also relates ~o he~bi
cldal compositions of matter comprising a herbicidally
effec~ive amount of a compound as described herein plus
--7--
an inert diluent or carrier suitable ror use with
herbicides~
As used herein, the term "herbicide" means a
compound which contro~s or modifies the growth of plants~
par~icularly of undesirable plants. By the term
'Iherbicidally effective amount" is meant an amount o~ a
compound which causes a controlling or modifying effect
on the growth of treated plants. The t:erm "plants" is
meant to include germinant seeds, emerging seedling~ and
established vegetation including roots and the above.ground -
portions. Such modifying and controlling effects include
all deviations from natural development, for example,
killing, retardation, defoliation, desiccation, regulation~
stunting, tillering, stimulation, dwaring and the :Like.
In general, the compounds of the present .Lnven-
tion can be prepared by the following methods:
I. An appropriate substitu~ed aniline (1) is
reacted with an acyl chloride (2) to produce the
corresponding substituted anilide ~3). The anilide is
chlorinated with phosphorus chloride to prepare the sub-
stituted phenyl containing imidoyl chloride (4). A
subsequent reaction with a secondary amine (4a) produces
a substituted ace~amidine (5) of th~ present invention.
This sequence of reactions is depicted by the following
equations:
I
~ NH2 + ClC-CM-A
(3) y 0
X~NH-C-G~-A ~ PC15
~ 9~
--8--
z Cl R_
\ CM-A ~ R2
B
\ /
(5) Y ~ ~ N
wherein A, B~ M, Rl~ R2, X~ Y and z have the same signi-
ficance as previously defined.
Reaction Scheme I
II. An alternative reaction scheme is ~he
reaction of an acylchloride (6) with a primary amine (7) to
produce the corresponding amide (8). This reaction is
followed by treatment of the amide (8) with phosphorus
pentachloride in phosphorus oxychloride as a sol~ent to
produce the imidoyl chloride (9). The imidoyl chloride is
reacted with a substi~uted aniline to produce the substi-
tuted acetamidine (lla) or (llb) of the present invention.
This sequence of reactions is depicted by the following
equations:
II
(6) ClC-CM-A ~ H N / 1 R2
B
~ 1
~1 / Rl or R2
(8~ A-CMCN
B ¦ ~ PC15(POC13 sol~ent)
~39075
g
z
(9) A-CM-C ~ ~ NH2 ~ (10)
B I NRl 2
~ 2
~Y
A-CM-C (lla)
B ~NRl or R2 .HCl
or
z
A-CM-C ~ (llb)
B ~ N-H
Rl or R2
wherein Ag B, M7 Rl, R2, X, Y and Z have the same signifi-
cance as previously defined
Reaction Scheme II
In reaction schemes I and II, some of the
individual reac~ions are performed in the presence of an
organic solvent, such as acetone, methylene chloride and the
like, where good chemical practice dictates. The reaction
temperatures can vary from -20C to 150C. In many
instances the reaction was exothermic. The reaction pressure
may be atmospheric, subatmospheric or superatmospheric.
However, for convenience of conducting the reactions, ~he
pressure is generally atmospheric. The reaction time will,
of course, vary depending upon the reactants and reaction
temperature. Generally, the reaction time is from 0.25 to
24 hours, depending upon ~he steps and rate of reaction.
After the reaction is co~ple~e, the product is recovered
by separation ~rom the by-products and the solvent removed
as by evaporation, or distillation. The structure is
~L~8g~5
-10-
confirmed by nuclear magnetic resonance or infrared spectra
The following are representative illustrative
examples for the preparation of the compounds o~ the present
invention and requisite intermediates therefor. Following
the examples isa table of compounds which are prepared
according to the described procedures.
EXAMPLE A
Intermediate Preparation:
3' 5'-Dichloro-dichloroacetanilide
.
81 grams (0.5 mole) 3,5-dichloroaniline was
dissolved in a flask containing 250 milliliters of reagent
grade acetone. The solution was cooled to 0C and 74 grams
(0.5 mole) dichloroacetyl chloride was added dropwise with
vigorous stirring with the rate of addition adjusted to
maintain the reaction temperature below 5C.
When the addition was complete, 51 grams (0.50
mole) of triethylamine was immediately added dropwise with
vigorous stirring, the addition rate adjusted to maintain
the reaction temperature below 5C. The reaction mixture
was then allowed to attain ambien~ temperature and stirred
at that temperature for one hour. The mixture was poured
into water, the solid product filtered off and dried giving
126 grams (92.3% yield) o~ the desired product, a white
solid, m.p. 133-135C.
EXAMPLE B
ntermediate Preparation:
3',5'-Dichlorophenyldichloroacetimidoyl chloride
121 grams (0.44 mole) 3',5'-dichloro-dichloro-
acetanilide and 100 milliliters of phosphorous oxychloride
were combined. Phosphorous pentachloride, 92.5 grams
(0.44 mole), was added and the mixture was stirred virorously
with heating at reflux until hydrogen chloride evolution
ceased. The phosphorous oxychloride was stripped off at
reduced pressure. Distillation gave 109 8 grams (85% yield)
g~5
o~ 3',5'-dichlorophenyldichloroacetimidoyl chloride con-
taining a small amount of solid. The b.p. was 122-126~/0.03
millimeters.
EX~MPLE lA
N-3' 5'-Dichlorophenyl-N'-isopropyldichloroacetamidine
10.2 grams (0.035 mole) 3',5'-clichlorophenyldi-
chloroacetimidoyl chloride was dissolved in a flask
containing 25 milliliters of methylene chloride and the
solution cooled in an ice bath. 4.5 grams (0.076 mole)
isopropyl amine was added dropwise while stirring vigorously
and temperature maintained below 15C. The reaction mixture
was stirred at ambient temperature one hour, and washed with
100 milliliters water. The organic layer was separated~
dried over magnesium sulfa~e and stripped at reduced pressure
to yield 10.7 grams (97.3% yield) of N-31,5'-dichlorophenyl-
N'-isopropyldichloroacetamidine, nD30 1.5653.
EXAMPLE C
Intermediate Preparation:
N-Isopropyldichloroacetamide
Dichloroacetyl chlori~e, 442.5 grams (3.0 mole),
was dissol~ed in a flask containing 900 milliliters of
methylene chloride and the solution cooled to 0C in an
ice/acetone bath. 354 grams (5.98 mole) of isopropyl amine
was added dropwise with vigorous stirring and the addition
rate was adjusted to maintaln the reaction temperature below
5C. When the addition was complete, the mixture was allowed
to stir at ambient temperature for one hour then washed with
2 X 500 milliliters water, the organic phase separated,
dried over magnesium sulfate and stripped of solven~ at
reduced pressure giving 499 grams (9~% yield) of ~he desired
product, a white sol~d, m.p. 45-4&C.
-12-
EXAMPLE D
Intermediate Preparation:
N-Isopropyldichloroacetimidoyl chloride
N-isopropyldichloroacetamide, 249.5 grams
(2.94 mole), and 210 milliliters of phosphorous penta-
chloride, 306.5 grams ~2.94 mole~, was added and the
mixture was stirred vigorously and heated at reflux until
hydrogen chloride evolution ceased. The phosphorous
oxychloride was stripped off at reduced pressure. Dis-
tillation at 4.5 millimeters gave 360 grams (65% yield)
of N-isopropyldichloroacetimidoyl chloride, b.p. 63~72C.
EXAMPLE lB
-
Preparation via N-isopropyldichloroacetimidoyl chlori~i
N-3',5'-Dichlorophenyl-N'-isopropyldichloroacetamidine
10.5 grams (0.065 mole) of 3,5-dichloroaniline
was combined with 14.7 grams (0.078 mole) of N-isopropyl
1~ dichloroacetimidoyl chloride in a flask and heated to 30C.
The reaction proceeded to 48C and was heated again until
it showed an exo~herm. External heating was stopped and the
reaction allowed to continue until it reached a peak exotherm
of 150C and then allowed to cool to ambient temperature.
While this reaction cooled, a second reaction using the
same amounts and reagents was performed. This reaction was
externally heated to 50C when it began to exotherm. A peak
temperature of 140C was reached while the reaction flask was
in an ice water bath. Both reaction mixtures were slurried
in acetone, combined and diluted with ether and the solid
hydrochloride iltered off. This yielded 42.2 grams
(92.7% yield) of solid m.p. 201-202C. The entire amount
was treated with 200 milliliters of 10% sodium hydroxide,
extracted with 2 X 250 milliliters methylene chloride~ the
organic layer dried over magnesium sulfate and stripped of
solvent under reduced pressure to give 36.5 gra~s (89% total
yield) of an oil, nD30 of 1.5672.
7~
-13-
~YAMPLE 2
N-3'~5'-Dimethylphenyl-N'-isopropyldichloroacetamidine
3,5-dimethyl aniline, 8.9 grams (0.073 mole), and
N-isopropyl dichloroacetimidoyl chloride, 15.8 grams
(0.084 mole), were combined in a flask an.d the temperature
immediately rose to 35C. An ice bath was applied, and
when the temperature reached 45C, acetone was added to the
bath. The exotherm cease~ a~ 115C, the ice bath was
removed and the flask h~ated to 120C and maintained at that
temperature until the mixture seemed homogeneous. A second
reaction was run in the same manner, both were allowed to
cool, slurried in ether, combined and filtered off as the
solid hydrochloride m.p. 201-203C. The hydrochloride was
then treated with 10% sodium hydroxide, extracted with
methylene chloride and the organic phase dried over magnesium
sulfate and the solvent stripped off at reduced pressure to
give 33.1 grams (82 8% yield) o~ the desired produce with an
nD30 1.5382
EXAMPLE 3
N-2,3-Dichlorop_enyl-N'-isopropyldichloroacetamidine
9.7 grams ~0.06 mote~ of 2,3-dichloroaniline was
combined with 13.6 grams (0.072 mole) N-iso~ropyldichloro-
acetimidoyl chloride and heated until the mixture started to
exotherm. An ice bath was used to control, but not stop,
the exothenm. After the exotherm peaked, the flask and its
contents were allowed to cool to a~bient temperature and
combined with a second reaction which was run in ~he same
manner. These combined reactions were slurried in acetone,
diluted with ether and the solid hydrochloride filtered off.
The solid was then treated with 10% sodium hydroxide,
extracted with methylene chloride, separated and the organic
phase dried over magnesium sulfate. The solvent was then
stripped off at reduced pressu~e to give 31.1 grams (82.7%
yield) of the desired produce, an oil, nD30 1.5668.
s
EXiMPLE 4
N-3-Chloro-2-methyl~henyl-N'-isopro~yldichlor~acetamidine
3-chloro-2-methylaniLine 9 10 grams (0.035 mole~,
and N-isopropyldichloroacetimidoyl chloride, 7.9 grams
(0.042 mole), were combined in a flask, heated to initiate
the reaction and the rate of exotherm controlled, but not
stopped, with the application of an ice bath. After the
exotherm subsided, the reaction flask was allowed to cool to
ambient temperature and the contents slurried with acetone
diluted with ether. The solid product was filtered off giv-
ing 10.0 grams (97.7% yield) of ~he hydrochloride which
decomposed at 236C. 5 grams (0.015 mole) of this hydro-
chloride was treated with 10% sodium hydroxide to give 4.3
grams (0.014 mole) of an oil, nD30 1.5440.
E~AMPLE 5
N-m-Trifluoromethylphenyl-N'-allyldichloroacetamidine
Allyl amine, 3 grams (0.053 mole), was dissolved
in a flask con~aining 25 millili~ers o~ methylene chloride
Meta-trifluoromethylphenyl dichloroacetimidoyl chloride,
7.6 grams (0.026 mole), was added dropwise while s~irring
and maintaining ambient temperature with a water bath. The
mixture was allowed to stir one houre, washed with water,
the organic phase separated and dried over magnesium sulfate
and the solvent stripped at~reduced pressure to give 6.9
grams ~85 2% yield) of an oil, nD30 1.4986.
EXAMPLE 6
N-m-Trif~uoromethylphenyl-N',N'-tetramethylenedichloro--
acetamidine
. .
Pyrrolidine, 3.6 grams (0.051 mole)~ was combined
in a flask with 25 milliliters of methylene chloride. Meta-
trifluoromethylphenyl dichloroacetlmidoyl chloride, 7.3 grams
(0.025 mole), was added dropwise while stirring and maintain-
ing ambient temperature with a water bath. The mixture was
allowed to stir one hour at ambient temperature, washed with
7~S
-15-
water, the organic layer dried over magnesium sulfate and
stripped of solvent to give 8.0 grams (98.8% yield) of an
oil, nD30 1.51~0.
EX~MæLE 7
4-(N-m-Trifluoromethylphenyl dichloroacetimidoyl~ morpholine
Morpholine, 4.2 grams (0.0482 mole), was combined
in a flask with 25 milliliters of methylene chloride. Meta-
trifluoromethylphenyl dichloroacetim-doyl chloride, 7 grams
~0.024 mole), was added dropwise while stirring and main-
taining ambient temperature with a water bath. The mixture
was allowed to stir at ambient temperature one hour 3 then
washed with water, the organic phase separated, dried over
magnesium sulfate and the solvent stripped off at reduced
pressure ~o give 7.3 grams (89% yield) of an oil, D30 1.5184.
EXAMPLE 8
3~N-m-TrifluoromethvlDhenvl dichloroace~imidoYl 2,2 S-tri
methyl oxazolidine
Twenty-two milliliters (0.048 mole) of a solution
of 2,2,5-trimethyl oxazolidine in benzene (4 milliliters =
1 gram in benzene) was combined in a flask with 15 milli-
liters o~ methylene chloride. Meta-trifluoromethylphenyl
dichloroacetimidoyl chloride, 6.7 grams (0.023 mole), was
added dropwise while stirring and maintaining ambient
temperature with a water bath. The mixture was allowed to
stir at ambient temperature one hour~ washed with water, the
organic layer separated, dried over magnesium sulfate and
stripped of solvent to give 6.5 grams (76.5% yield) of an
oil, nD30 1.4818.
EXAM_ 9
Preparation of Intermediate.
N-Iso ro 1 chlorofluoroacetamide
P PY
A solution of 11.8 grams (0.2 mole) isopropyl amine
in 20 milliliters ethyl a~cohol were added dropwise a~
1~9(~
10-15C with stirring to a solution of ethyl fluorochloro-
acetate and 5 drops of ethylene glycol in 80 milliliters
ethyl alcohol. The solution was stirred at 10-20C for 2
hours and was then stored at -15C for 3 days. At this
time, the solution was evaporated to leave a liquid, 25.2
grams, nD30 1.43g5, identified as the title compound by
infrared and nuclear magnetic resonance spectroscopy~
Preparation of Intermediate:
N-Isopropyl chlorofluoroacetamide
In a 100 milliliter flask were placed 22 grams
(0.14 mole~ of N-isopropyl chlorofluoroacetamide and 3
milliliters of phosphorous oxychloride. Pulverized phos-
phorous pentachloride9 30.0 grams (0.14 mole), was added to
this mixture at an initial temperature of 32C. The
temperature rose to 42C over the course of the addition.
After all the phosphorous pentachloride had been added, the
mixture was heated. The majority of the hydrogen chloride
was evolved at 40C and by the time the temperature reached
re~lux (120C), gas evolution had ceased. The mixture was
next distilled at atmospheric pressure using a 15 centimeter
glass - helix packed column with attached variable takeoff
condenser to give 17.8 grams of product, b.p 136-138C,
identified as the title compound by infrared and nuclear
magnetic resonance spectroscopy.
N-(3 2 5-Dimethylphenyl)-N'-isopropyl chlorofluoroacetamidine
In a 100 milliliter flask was placed 5.0 grams
(0.03 mole) of N-isopropylchlorofluoroacetimidoyl chloride.
A thermometer and air-cooled condenser were attached to the
flask. To this was added 2.8 grams (0.02 mole) of 3,5-
dimethylaniline. There was an immediate increase in tem-
perature and formation of a whi~e solid. I~hen the
temperature reached 70C, a cold bath was applied to moderate
the reaction and when no further isotherm was observed, t~e
mixture was heated to 140C with a heat-gun.
The mixture was then allowed to return to room
1~890~5
-17-
temperature and the resulting dark oil was taken up in
acetone, addition of pentane caused a solid tQ separate
which was removed by filtration. This solid was mixed with
50 milliliters methylene chloride and shaken with 50
milliliters of 10~/~ sodium hydroxide. The organic layer was
separated, washed twice with 50 milliliters portion of
water and dried over magnesium sulfate.
Removal of solvent in vacuum lef~ an oil, 3.6
grams, nD30 1.5229, which was identified by infrared and
nuclear ma~netic resonance spectroscopy to be the title
compound. The oil eventually crystallized to a solid of
m p. 37-40C.
~XAMPLE 10
N-C~3-Dichlorophenyl)-N'-isopropyl chlorofluoroacetamidin_
The above procedure was repeated with 5.0 grams
(0.03 mole) N-isopropylchlorofluoroacetimidoyL chloride and
3.7 grams (0.02 mole) of 2,3-dichloroaniline to yield 3.7
grams of a dark oil, identified by infrared and nuclear
magnetic resonance spectroscopy to be the title compound.
~XA~LE 11
N-(3~5-Dichlorophenyl)-NI-isoprop2~ chlorofluoroacetamidine
The above procedure was repeated with 5.0 grams
(0.03 mole) N-isopropylchlorofluoroacetimidoyl chloride and
3.7 grams (0.02 mole~ of 3,5-dichloroaniline to yield 4.9
grams of an oil, nD3 1.55409 identified by infrared and
nuclear magnetic resonance spectroscopy as the title com-
pound.
EXAMPLE 12
Preparation of Intermediate:
N I30FIropylbr~mofluoro acetamide
A solution of 14.8 grams ~0.25 mole) isopropyl
amine in 25 milliliters ethanol was added dropwise to a
solution of ethyl bromofluoroacetate, 40 grams (0.22 mole),
-18-
and 5 drops ethylene glycol in 100 milliliters ethyl alcohol
at 10-15C. The solution was stirred at 10-20C for 2 hours
and was then stored at -15~C for 3 days. At this time, the
solution was evaporated to leave a liquid, 41.8 grams,
nD30 1.4629, identified by infrared spectroscopy as the title
compound.
Preparation of Intermediate:
N-Isopr pylbromo1uoroacetimidoyl bromide
-
In a lO0 milliliter flask fitted with a gas-inlet,
10 thermometer, magnetic stirrer and reflux condenser were
placed 20.0 grams (0.1 mole) of N-isopropylbromofluoro-
acetimidoyl bromide Argon was flushed through the system
and after 15 minutes, 27.3 grams (0.1 mole) of phosphorous
tribromide were added in one portion. The temperature rose
15 to Q8C. Cooling was applied with an ice bath and bromide,
1.1 grams (0.1 mole) was added slowly with stirring. ~ter
addition was complete, the mixture was allowed ~o come to
room temperature and after one hour it was heated to 85-90C.
The argon purge was maintained throughout the heating period.
20 After 1 1/2 hours the evolution of HBr had ceased and the
mixture was cooled to lO~C and filtered free oX phosphorous
oxybromide. The filtrate was vacuum distilled to yield
16.4 grams, b.p. 53-60C at 1 millimeter. Identified by
infrared spectroscopy as the title compound.
25 N-(3,5-Dichlorophenyl)-N'-isopropyl bromofluoroacetamidine
In a 100 milliliter ~lask was pLaced 5.0 grams
(0.02 mole) of the above lmidoyl bromide. A thermometer and
air cooled condenser were attached to the flask. To this
was added 3.1 grams ~0.02 mole) of 3,5-dichloroaniline. The
30 temperature rose slowly to 70C, and at 70C an ice bath was
used to moderate the reaction. ~en no further exotherm was
observed, ~he mixture was heated to 135~C and was then al-
- lowed ~o cool. The residue was taken ~p in 50 milliliters
methylene chloride and this solution was carefully shaken
35 with 50 milliliters of 10% sodium hydroxide solution. ThP
9~
-19 -
organic layer was then shaken wi~h 50 milliliters of a
saturated salt solution and dried. Removal of solvent in
vacuum left an oil, 2.9 grams, identified by infrared and
nuclear magnetic ~esonance spec~roscopy as the title
compound.
EXAMPLE 13
Preparation of Intermediate:
N-Isopropyldifluoroacetamide
A solution of 20 grams (0.16 mole) of ethyl
difluoroacetate in 20 milliliters ethyl alcohol was added
slowly in a solution of 9.5 grams (0.16 mole) isopropyl-
amine and 5 drops of ethylene glycol in 30 milliLiters ethyl
alcohol. The temperature rose slowly to 27C. The mixture
was then refluxed for 3 days. After this reflux period, the
solution was evaporated at 100 millimeters and the residue
was distilled at atmospheric pressure to yield 18.0 grams,
b.p. 86-88, identified by infrared spectroscopy as the
title compound
N-Isopropyldifluoroacetimidoyl bromide
In a 100 milliliter flask fitted with thermometer,
gas-inlet, and magne~ic s~irrer was placed 12.0 grams (0.09
mole) of N-isopropyldifluoroacetamide. Argon was flushed
through the system and phosphorous tribromide, 27.3 grams
~0.09 mole), was added slowly at 10-15C. Bromine, 14.0
grams (0.09 mole)~ was then added slowly at 10-15C with
~5 s~irring. After all the bromine was added~ the mixture was
allowed to come to room temperature and was then heated with
argon sweep at 85-90C Heating was continued ~or 2 hours.
The mixture was next cooled to 0C and filtered free of
phosphorous oxybromide. The ~iltrate was vacuum distilled
to yield 4.0 grams, b.p. 34 38 (50 millimeters identi-
fied by infrared spectroscopy as ~he title compound.
-20-
N-(3,5-DichloroPhenyl)-N-isopropyldifluoroacetamidine
A solution of 3.2 grams (0.02 mole~ of 3,5-
dichloroaniline in 50 milliliters toluene was heated to
reflux (111C) and 4.0 grams (0.02 mile) of N-isopropyldi-
fluoroacet~nidoyl bromide was added slowly. A vigorous
reaction occurred with separa~ion of solid. The mixture
was refluxed for 1/2 hour after addition was complete,
cooled and filtered to give 6.0 grams of the hydrobromide
sal~. The solid was slurried in 50 milliliters methylene
chloride in a separatory funnel and this mixture was shaken
with cold 5% sodium hydroxide solution. The mixture was
phase-separated and washed with two 50 milliliter portions
o~ water. Evaporation of solvent after drying leEt 3.9
gr~ms of a liquid, nD30 1.5425, identified by infrared and
nuclear magnetic resonance spectroscopy as the title com-
pound.
Dichloroacetamidine Salt Examples
EXAMPLE 14
Trifluoroacetic Acid Salt of N-(3,5-Dichlorophenyl)-N'-
isopropyl dichloroacetamidine
The amidine (3.1 grams~ 0.01 mole) and the
trifluoroacetic acid (1.1 grams, 0.01 mole) were combined
in 35 millili~ers ethyl ether and the mixture allowed to
stir ov~rnight at room temperature, refluxed for 45 minut2s
and the solvent removed in ~acto. The product was a very
viscous semi-solid. Yield: 2.0 grams (47.6%). Infrared
indicated the product was the expected salt.
EXAMPLE 15
Composition of Pivalic Acid and N-~3,5-Dichlorophenyl-N'-
isopropyl dichloroacetamidine
The amidine (3.1 grams, 0.01 mole) and pivalic
acid (1.0 grams, 0.01 mole) were combined in 35 milliliters
tetrahydrofuran. The mixture was stirred 1/2 hour at room
-21^
temperature and refluxed 2 hours. The solvent was removed
giving a tan oil, nD3 1.5192. Yield: 4.0 grams (97.5%).
Infrared indicated a composition of pivalic acid and amidine.
EXAMPLE 16
Com~osition Df 10-Undecenoic Acid and N-(3 ? 5-Dichloropheny~
N'-iso ro 1 dichloroacetamidine
P PY
Sa~e procedure as in Example 15. There was
ob~ained a tan oil, nD30 1.5163. Yield: 4.5 grams ~91.8%).
Infrared confirmed the expected title composition.
EX~MPT ,F_1 7
Composition of Succinic Acid and N-(3,5-Dichlorophenyl)-N1-
iso ro vl dichloroacetamidine
P P, _ _
Same procedure as in Example 15 using the acet-
a midine (3.1 grams, 0.01 mole) and succinic acid (0.6 grams,
O.OOS mole). Viscous semi-soLid. Yield: 2.1 grams
(56.8%). Infrared confirmed the expected title composltion.
The following is a table of compounds which are
prepared according to the aorementioned procedures. Com-
pound numbers have been assigned to them and are used for
identification throughout the balance of the specification.
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-25-
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-32-
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-34-
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-36-
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-38- 3L~9~5
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-39-
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-45-
HE~BICIDE SCREENING TESTS
As previously mentioned, the herein described
compounds produced in the above-described manner are
phytotoxic compounds which are useful and valuable in con-
trolling v~rious plant species. Compounds of this inven~ion
were tested as herbicides in the following manner.
A._ Pre-emergence Herbicide Screening Test
Using an analytical balance, 300 mill~grams of the
compound to be tested is weighed on a piece of glassine
weighing paper. The paper and compound are placed in a
2 oz. amber bottle and dissolve in 45 milliliters o~ acetone.
If the material is not soluble in acetone, another solvent
such as water, alcohol, or dimethylformamide (DMF) is used.
When DMF is used, only 1.5 milliliters o less are used to
dissolve the compound and then another solvent is used to
bring the volume to 45 milliliters. Twenty millill~ers o
this solution ~g transferred to a 80 m~llillter wide~mouth
amber bottle and diluted with 24.5 milliliters o~ a water and
acetone mixture (lO:l) containing 1% Tween 20 ~ (polyoxy-
ethylene sorbitan monolaurate). The solution is sprayed on
the seeded flat on a linear spray table calibrated to deliver
80 gallon per acre, the application rate is 2 lb/acre
~2.24 kg/hectare).
When applied at 8 lb/acre (8 . 96 kg/hectare), 20
milligrams of the compound to be tested are weighed onto a
glassine weighing paper, placed into a 30 milliliter ~ial,
and dissolved in 3 milliliters acetone containing 1%
Tween 20 ~. If the material is not soluble in acetone,
another solvent such as water, alcohol, or dimethylformamide
(DMF~ is used. When DMF is used, only 0.5 milliliters or
less are used to dissolve the compound and then another
solvent is used to bri~g the volume to 3 milliliters. The
solution is atomized onto the seeded fla~ using a No. 152
De~ilbiss atomizer at a pressure of 5 lb/square inch
(0.35 kg/cm2), and the spray volume was 143 gallons per
acre (1338 liter per hectare).
s
-46-
On the day preceeding treatment, a flat is filled
with sandy loam soil fortified with 50 ppm 17-17-17 erti-
lizer and Captan ~. Seven rows are Lmpressed across the
width of the flat and seeded with one species per row. The
sePds are covered with soil so that they are planted at a
depth of 1.2 centimeters. The species are hairy crabgrass
~CG) (Dig~taria san~uinalis), foxtail (FT) (Setaria spp ),
watergrass (WG) ~Echinochloa crus~ali), wild oat (WO)
tAvena fatua), mustard (MD) (Brassica juncea), curly dock
(CD) (Rumex crispus), and pigweed (PW) (Amaranthus
retro~lexus~ is seeded between the last row and the end of
the flat at a depth of 1 centimeter. Ample seeds are
planted to give about 20 to 50 seedlings per row after
emergence depending on the size o~ the plant at the time of
rating. At the 8 lb/acre testing rate red oat (RO) (~ena
sativa) is used instead of wild oat.
~fter treatment, the ~lats are placed in the green-
house at a temperature of 70 ~o 85F and water by
sprinkling. Two weeks after treatment the degree of lnjury
or control is determined by comparison with untreated plan~s
of the same age. The injury rating is recorded as 0 to 100%
for each species where 0 represents no inju~y and 100%
represe~ts complete kill.
B. Post-emergence Herbicide Screening Test
The procedure for this test is substantially the
same as the pre-emergence herbicide screening test A. The
seeds of the plant species or the 2 lb/acre test are
described in screeninO test A. The seeds for ~he 8 lb/acre
post-emergence test included: hairy crabgrass, watergrass,
red oat, mustard, curly dock and pinto beans (BN) (Phaseolus
vulgaris). The flats are seeded and placed in the greenhouse
8-12 days prior to treatment with the candidate compounds.
The plan~ foliage was sprayed with solutions v~ the candidate
compounds.
For the 8 lb/acre solutionS 20 milligrams of the
test compound was weighed out and dissolved as described
-47-
above except that 2.5 milliliters acetone with 1%
Tween 20 ~ or other suitable solvent plus 2.5 milligrams
o water was atomized as described above. The spray volume
was 238 gallons per acre (2226 liters per hectare). The
rate at 2 lb/acre (2.24 kg/hectare) was achieved using the
linear spray table as described above.
The results of these tests are shor~n in Table II.
'75
-48 -
TABLE II
Herbicida~ Activity - Screening Results
Percent Control a~ 8 lb/A
. .
Compound Pre emergenc e Pos t - ernergenc e
N~er CG F~G R0 PW Mi) CD CG WG R0 ~ CD BN
90 80 8(~ 0 0 0 0 0 0 () 0 0 0
90 80 $() 70 0 0 0 0 0 0 0 (3 0
3 ~ 0 0 0 0 0 0 80 70 0 100 80 40
~, o o o o o o o o o o 100 0 0
100 80 80 60 0 0 0 80 70 70 0 0 0
6 80 80 80 60 100 30 20 0 0 0 0 0 0
7 40 40 0 0 0 0 0 0 100 0 0
8 0 0 0 0 0 0 0 20 0 0 0 0 10
9 0 0 0 0 30 0 20
0 0 0 0 0 0 0 0 0 0 80 0` 0
11 0 0 0 0 0 30 0 100 95 30 lO0 ~0 ~0
12 0 0 0 0 0 0 0 95 20 10 0 0 0
~3 100 99 99 90 45 20 45 95 95 0 0 20
1~ 99 96 95 30 0 0 35 95 95 0 0 20 0
99 ~8 98 99 0 0 65 98 95 10 0 2~ 0
16 80 80 90 20 0 0 0 0 0 0 0 0 0
17 98 98 98 60 40 20 90 95 95 0 0 20 10
18 95 95 90 95 0 0 ~5 95 95 0 0 20 10
~9 80 80 60 1~ 0 0 0 95 95 0 o 0 0
80 80 80 0 35 20 ~0 95 6~ 0 20 20 10
21 0 0 0 0 0 ~ 0 0 0 0 10 0 0
22 0 0 0 0 0 0 0 0 0 0 10 0 0
~3 0 0 0 0 0 0 0 0 0 0 50 0 0
~4 ~ 40 4û 0 20 10 20 95 80 0 0 30 10
~9~)7~;
-49-
TABLE II (Cont'd)
Compound Pre-emer ence Post-emergence
~umber CG FT WG Rg PW MD CD CG WG R0 MD CD BN
0 0 0 0 0 0 0 0 0 0 0 0 10
26 0 0 0 9~ 60 0 0 0 0 0 0 0
27 0 0 0 0 0 0 0 0 0 0 0 0 70
28 0 0 0 0 80 60 60 20 0 0 20 0 0
29 0 0 0 0 0 95 0 0 0 0 0 0 4
0 0 0 0 80 60 0 0 0 0 0 0 0
31 0 0 0 0 98 30 40 0 0 0 0 0 0
32 0 0 0 0 0 0 0 4~ 40 0 0 0 0
33 95 90 80 0 50 90 0 0 0
34 40 90 0 0 0 20 0 0 0 0 0 0 0
0 0 0 0 0 0 0 lO0 60 20 0 0 0
36 0 0 0 0 0 0 0 90 50 20 70 0 60
37 95 30 20 0 0 0 0 0 0 0 0 0 0
38 0 0 0 0 95 60 50 0 0 0 0 0 0
39 98 95 80 0 20 40 30 30 30 0 30 0 60
0 0 0 0 80 ~0 0 0 0 0
41 98 98 80 0 60 20 30 0 0 0 0 0 0
42 0 0 20 10 100 30 20 0 0 0 0 0 0
43 100 99 98 0 97 70 90 100 95 30 100 40 40
44 98 99 98 30 97 50 95 95 90 30 98 50 20
98 99 95 80 70 0 40 95 80 50 90 S0 40
46 100 99 98 60 98 40 ~5 ~5 80 30 40 40 50
47 99 99 97 30 95 30 95 95 90 40 90 60 50
48 99 99 80 0 40 0 20 95 80 30 50 40 40
4g 100 9g 9~ lO 97 ~0 70 90 80 3~ 50 50 50
99 99 98 2~ 30 0 20 95 80 60 70 60 10
39~37
-50-
TABT.E II ~Cont ' d~
Compo~dPre-emer~ence Post-emer ence
NumberCG F~O~I~ MD CD CG_W(~ BN
51 99 98 60 70 0 0 30 98 80 20 30 40 0
52 98 98 ~0 30 50 20 60 98 80 40 40 4050
53 100 100 98 20 60 40 80 98 80 40 4050 50
54 30 0 0 0 0 0 0 0 0 0 0 0 0
90 30 30 0 95 0 0 0 0 ~ 0 0 0
56 20 10 20 0 0 0 0 0 0 0 0 0 0
57 98 98 98 80 80 0 30 98 70 30 0 0 40
58 1~0 98 98 0 80 20 70 95 95 30 3020 0
59 o o o o o o 0 95 80 0 0 0
g8 95 95 0 0 0 0 40 20 0 0 0~ 30
61 99 98 80 80 80 20 60 98 95 95 0 0 30
62 97 95 95 0 0 0 0 9~ 80 0 100 40 10
63 100 100 100 100 80 20 100 0 0 0 0 0 0
~4 100 100 100 95 80 10 80 0 0 0 0 0 20
100 100 lO0 97 50 ~0 95 0 0 0 0 0 20
66 100 100 100 99 98 70 98 20 0 30 0 0 20
67 100 99 99 0 0 0 0 0 0 0 0 0 0
68 100 100 99 98 30 30 90 0 0 0 0 0 0
69 100 100 99 95 80 0 98 0 0 0 0 0 0
100 100 99 20 30 20 40 40 0 0 10 0 20
71 10~ 100 99 0 0 ~0 30 0 0 0 20 3030
72 100 95 go 30 0 0 0 0 0 ~ o o o
73 100 90 95 40 0 0 0 0 0 0
74 100 g8 98 ~0 20 0 0 90 40 20 20 0 30
100 100 100 50 99 50 80 98 9~ 20 2030 40
76 100 100 100 20 g~ 20 0 98 gO 0 0 20 10
-51-
~ABLE II (Con~ ' d2
Cor~3o~dPre-emer ence Post-emer ence
NumberCG F'l` WG R~ P~J MD CD CG ~ R0 ~CD BN
77 ~ 00 99 99 0 80 10 20 90 60 0 0 0 30
78 100 98 98 0 10 20 0 30 30 0 0 ~ 2~
79 100 100 10~ ~0 80 20 90 0 0 0 0 0 10
80 40 95 0 0 0 0 0 0 0 0 0 0
81 100 ~00 100 0 98 80 90 9~ 60 0 10 20 30
82 ~00 99 99 0 95 40 70 80 80 0 20 20 40
83 100 100 100 10 98 40 98 95 80 20 30 40 40
84 100 100 99 10 80 50 ~5 95 90 0 20 30 40
0 0 0 0 0 0 0 0 0 0 10 0 0
86 98 98 80 0 30 0 10 90 70 10 30 20 40
87 98 98 50 0 0 0 0 95 80 10 30 30 ~0
88 100 100 95 0 70 0 20 95 80 0 10 30 40
89 100 99 95 0 20 0 0 95 10 0 30 30 40
98 20 20 0 0 0 0 60 0 0 70 20 20
91 100 100 100 90 99 95 95 ~8 95 ~0 80 80 8~
92 100 100 100 70 98 90 95 95 80 40 60 80 40
93 100 100 100 92 98 95 98 98 80 80 95 95 80
94 100 100 99 20 90 90 98 95 98 90 9~ 9S 80
100 100 99 30 95 80 90 95 80 80 70 80 70
96 100 100 99 20 95 40 gO 95 80 20 40 80 40
97 100 98 40 0 9S 0 0 98 80 20 20 80 30
98 1~0 99 ~9 20 97 10 60 95 60 0 10 ~ 30
99 100 98 98 20 60 30 50 g5 80 1~ ~0 80 40
100 100 100 100 80 9~ 10 80 98 8¢ ~) 0 90 40
101 100 98 99 30 g8 10 50 9~ 70 10 ~0 80 30
102 99 99 97 20 98 0 20 98 95 0 30 80 40
-52 -
TABLE II (Cont ' d)
Compo~mdPre - emer~;enc e Pos t - emer~;enc e
NumberCG FT WG R0 P'W ~D CD CG WG R0 2~[) eD BN
103 99 98 95 60 99 3~) 70 95 70 20 10 30 40
104 90 50 40 20 10 0 0 0 10 0 10 0 0
105 99 3t3 20 10 98 0 0 0 ~) O 10 0 0
106 ~00 100 99 20 95 40 50 9~ 90 40 ~00 60 3V
107 95 90 ~0 10 0 0 0 70 ~ O 30 0
108 9~ 97 97 20 98 10 30 99 60 10 20 30 40
109 0 0 0 ~ 0 0 0 80 10 0 30 0 0
110 100 50 80 30 0 0 0 30 0 ~ 10 0 0
111 95 40 70 20 95 0 0 0 0 0 20 0 0
1~2 98 40 40 0 60 0 0 0 0 0 10 0 0
1~3 70 20 20 0 0 10 0 0 0 0 0 0 0
11~ 100 ~9 99 97 ~0 0 70 98 90 10 0 60 40
llS 100 99 99 40 30 20 80 98 95 80 0 100 40
116 99 98 98 70 20 20 40 98 95 0 10 40 40
117 100 98 98 60 10 20 10 9S 60 10 30 100 50
11~ 99 98 95 0 0 0 0 98 30 20 0 0 30
119 98 98 95 30 0 0 0 ~ 10 0 0 30 ~0
120 99 97 98 30 20 0 10 ~8 80 20 0 50 40
121 100 9~ ~7 80 0 0 0 99 98 30 0 98 30
122 0 0 0 0 0 100 0 0 0 0 100 0 0
123 30 0 30 30 60 30 40 90 70 10 0 0 0
~24 99 97 98 80 0 0 40 70 30 0 0 0 0
125 100 100 100 100 98 80 60 98 90 20 30 98 60
126 100 100 100 99 98 80 95 98 90 30 30 60 60
127 - 100 10{) 99 99 95 99 - 9~) 0 40 40 ~0
128 - 100 100 99 98 9~ 99 - 80 10 40 40 `40
7S
-53~
TABLE II (Con~ ' d)
Compo~d Pre-emer~ence Post-emer ence
Number CG FT WG R0 PW MD CD CG W(~ RO ~ cb BN
129 ~ 100 100 9S 9~ 40 ~8 - ~û 0 0 0 10
130 - 100 99 95 80 0 95 - 40 0 0 40 30
131 - 9~ 98 20 80 60 70 - 0 0 0 0 10
132 - 100 99 90 30 20 70 - 0 0 0 0 20
133 - 90 98 30 0 0 0 - 0 0 0 0 0
134 100 100 9g 95 20 40 - 40 10 0 0 30
135 - 0 0 0 0 0 0 - 0 0 0 0 10
136 - 98 95 lO 0 0 0 - 0 0 0 0 0
137 - 40 40 0 0 0 0 - 0 0 0 0 0
138 - 95 98 40 80 20 0 - 70 0 0 0 0
139 - 96 97 60 0 0 0 - 0 0 0 0 0
140 - 99 98 40 0 0 0 - 0 0 0 0 0
141 - 98 98 30 80 0 0 - 40 0 0 0 20
142 - 100 100 40 30 0 0 - 70 0 0 0 0
143 - 100 100 40 30 10 0 - 40 0 0 0 20
144 - 100 ~00 100 98 98 95 - 80 0 30 0 30
145 - lO0 100 97 95 95 98 - 80 0 0 0 40
1~6 - 80 95 10 0 0 0 - 0 0 0 0 0
147 - 30 40 0 0 0 0 - 0 0 0 0 0
148 - 100 100 97 98 97 99 - 8S 20 70 40 20
149 - 100 ~00-97 98 97 99 - 80 0 30 0 7Q
lS0 - 100 100 40 ~0 3~ 0 - 60 0 30 0 0
151 - 100 100 10 0 0 0 - 75 0 30 0 50
152 - .100 99 70 20 0 0 - 60 0 30 0 0
153 - 100 100 98 40 30 8û - 95 0 40 0 60
154 - 100 100 40 10 50 60 - 20 0 0 0 30
5~
TABLE II (Cont ' d~
Compo~dPre-emer~nce Post-emergence
NumberCG FT WG R0 _ PW MD CD _CG WG R0 MD CD BN
155 - 100 100 70 90 90 90 - 20 0 20 0 20
156 - 0 0 0 0 0 0 - 30 0 0 0 20
157 - 100 100 83 80 80 98 - 95 40 70 60 30
158 - 100 100 98 98 98 98 - 95 0 30 0 50
159 - 4~ 50 20 0 0 0 - 0 0 0 0 0
160 - 98 100 40 30 10 80 - 0 0 0 0 0
161 - 100 100 95 40 50 0 - 85 10 70 0 0
162 - 100 100 100 0 80 20 - 90 20 0 0 40
163 - 100 100 0 20 20 0 - 20 0 0 0 0
164 - 100 100 20 0 0 0 - 80 0 20 20 0
165 -' 100 ~00 ~00 50 70 20 - 30 20 10 0 0
166 - 100 ~00 100 80 80 80 - 90 30 0 0 ~0
167 - 90 70 0 0 0 0 - 0 0 0 0 0
168 - 80 70 0 0 0 0 - O O û 0 20
169 - 100 98 30 40 0 40 - g5 0 30 ~0 50
170 - 100 99 40 50 30 50 - ~5 20 ~0 ~0 60
171 - 98i g8 98 0 0 0 - 60 0 0 0 0
172 - 9898 40 0 0 0 - 70 0 0 0 0
173 - 9530 0 0 0 0 - 20 0 0 0 0
174 - 9860 20 0 0 0 - 40 0 0 0 10
175 - 9~98 30 0 0 0 - 60 10 0 0 0
176 - 9998 ~) 40 0 20 - 70 1~ 0 0 10
177 - 100 100 20 90 30 20 - 98 20 10 10 20
17~ - 98 98 30 97 0 20 - 90 30 0 0 0
179 - 9~ 70 0 0 0 0 - 60 0 0 0 0
180 - 9999 10 ~0 20 3~) - 95 0 20 ~ 0
v~
-55-
TABLE II (Cont'd~
Compound Pre emer~ence Post-emer~ence
Number CG FT WG R0 PW Ml) CD_ CG li~G R0~ P~ ~ BN
181 - 30 50 20 90 100 0 - 90 98 10~ ~00 100
182 - 100 100 80 40 30 70 - 0 0 0 0 0
Percent Control at 2 lb/A
CQmpound Pre~emergence Post-emergence
Number CG FT WG W0 MD CD PW CG FT WG W0 MD CD PW
183 - 80 98 80 lO 0 10 - 80 B0 20 20 0 10
1~4 - 100 100 100 10 98 90 - 99 95 70 100 98 100
185 - lO0 100 ïO0 98 g9 100 - 80 90 20 ~0 30 0
~86 - 20 10 10 0 0 0 - 0 0 0 0 0 0
187 100 100 10 0 20 0 - 80 90 10 50 50 20
18~ -' 99 96 80 0 0 0 - 20 20 0 0 0 0
189 - 100 98 .40 0 0 0 - 50 40 0 0 0 0
190 - 0 20 0 0 0 0 - 0 ~ 0 0 0 0
191 - 98 98 20 0 40 0 - 60 80 0 0 0 0
192 - 100 100 80 20 80 60 - 80 80 10 0 0 0
193 - 100 lO0 60 0 0 0 - 30 40 0 0 0 0
194 - 20 ~0 0 0 0 0 - 0 0 0 0 0 0
195 ~ 20 60 0 0 0 0 - 0 0 0 0 0 0
196 - 0 0 0 0 0 0 - 20 0 0. 0 0 0
197 - 10 10 0 0 0 0 - 0 0 0 0 0 0
1~8 - 40 60 0 0 0 0 - 20 20 0 0 0 0
199 - 100 100 7~ ~0 9~ 40 - 90 90 30 4~ 40 30
200 - 0 0 0 0 0 0 - 80 60 0 lO 70 20
201 - 30 80 10 0 0 0 - 80 80 20 30 30 10
20~ - 0 0 0 0 0 0 - ~0 40 0 ~0 70 40
9~7~i
-5~-
TABLE II (Cont'd~
Compound Pre-emergence Post~emergence
Number CG FT WG W0 MD CD PW CG FT WG W0 MD_ CD PW
2~3 - 100 100 98 30 9~ 0 - 90 80 20 30 50 50
204 - 100 100 90 30 80 0 - 90 80 20 30 60 ~
205 - 100 100 80 0 90 9~ - 710 ~0 20 20 30 20
~06 - ~0 100 80 g5 98 30 - 80 80 10 30 20 100
207 - lOd 100 80 60 100 100 - 80 80 80 40 60 20
208 - 100 100 60 20 100 100 - 80 60 0 0 0 0
209 - ~0 0 0 50 60 90 - 0 0 40 40 60 40
210 - 100 100 100 60 100 100 - 0 0 0 0 0 0
211 - 98 98 70 0 80 80 - 60 40 50 60 75 60
21~ - 70 50 0 0 40 0 - 60 0 0 70 70 60
Percent Control at 8 lb/A
CompoundPre-emer ence Post~emergence
NumberCG F~ WG Rg P~ MD CD CG WG R0 MD CD BN
213 98 99 9~ 40 0 0 40 95 9S 20 10 20 30
214 100 100 100 20 90 30 85 g5 90 0 0 20 50
215 100 lOQ 100 98 80 60 95 100 95 20 0 0 50
216 100 100 100 ~0 80 30 80 100 9~ 0 0 0 ~0
217 100 99 99 50 90 10 60 0 0 0 0 0 0
218 100 99 99 99 90 10 80 90 80 0 0 0 20
219 100 100 100 100 90 60 80 95 90 20 0 0 0
220 100 100 100 98 98 20 90 20 0 0 60 0 20
221 100 100 100 70 90 60 95 98 90 0 ~0 30 50
222 100 100 100 98 99 97 98 ~ 80 70 40 80 98
223 99 97 98 ~0 30 0 60 ~00 90 0 0 100 ~)
224 ~00 98 98 95 50 30 40 98 90 20 10 40 40
-57-
TA:BLE II ~Con~ ' d)
Compound Pr~emer~enpl/~ ~ CD P st-~ e
225 100 99 ~5 60 30 0 40 98 95 20 10 40 40
226 98 98 80 0 0 0 0 98 30 0 30 40 50
227 g8 98 30 0 0 0 0 80 20 0 0 0
228 98 98 95 20 0 0 0 9~ 30 0 0 ~ 30
2~9 9g 98 98 98 ~ 0 0 99 90 30 0 50 30
230 ~8 80 80 80 0 0 0 98 90 10 0 100 40
231 0 0 o o o o o go o o o o o
232 98 96 98 97 0 0 0 95 70 20 0 30 30
233 100 100 100 98 70 70 60 98 80 10 40 20 40
234 100 100 100 99 99 95 90 98 95 20 30 100 80
235 - 100 100 95 90 95 99 - 80 10 50 60 20
236 - 100 100 99 99 96 99 - 85 20 40 40 50
237 - 99 99 40 95 30 95 - 60 0 0 0 5
238 - 100 100 95 40 30 90 - 80 0 0 40 40
239 - 95 98 20 80 60 70 - O û 0 0 10
240 - 100 100 95 40 60 90 - 30 0 0 100 40
241 - 80 g5 0 0 0 0 - 0 0 0 0 10
242 - 100 100 98 95 10 80 - 30 0 0 0 30
243 - 0 10 10 0 0 0 - 0 0 0 0 10
244 - 40 4~ 0 0 0 0 - 0 0 0 0 0
245 - 95 95~ 10 0 0 ~ - 0 0 0 0 0
246 - 90 98 20 60 0 0 - 60 ~ 0 30
247 - 99 95 40 30 0 0 - 0 0 0 0 0
248 - 30 0 0 0 0 0 - o o o o o
249 - 9~ 98 40 0 0 0 - ~0 0 0 0 10
250 - 99 ~00 0 30 40 ~0 - 60 0 0 0 0
-58-
TABLE II ~Con~ ' d)
Compound ~re-emer~ence ~
Number_ CG FT WG R0 PW MD CD CG WG R0_MD CD BN
251 -98 97 40 0 0 0 - 60 0 0 0 40
252 -100 100 98 80 90 97 - 70 0 40 0 20
253 -100 100 10~ 98 98 98 - 70 0 30 0 40
254 -80 70 30 0 0 0 - 0 0 0 0 0
255 -80 70 40 0 0 0 - 20 0 0 0 40
256 -100 100 99 98 98 98 - 80 0 40 30 30
257 -100 100 100 99 98 98 - 70 0 30 0 50
2~8 -100 100 30 0 0 0 - 40 0 0 0 0
259 100 100 30 20 0 0 - 70 0 30 0 50
260 -100 100 50 80 60 80 - 60 0 30 0 30
261 -100 100 40 60 50 30 - 70 0 20 0 60
262 -100 100 60 80 60 95 - 0 0 0 0 30
263 -.100 100 70 90 90 95 - 30 0 0 0 20
2~4 -0 40 10 0 0 0 - ~ 0 0 0 0
2 65 -98 98 97 0 ~ 0 - 0 0 0 0 0
266 -100 100 98 80 80 98 - 80 0 50 0 30
267 -lO0 100 90 60 80 95 - 80 0 S0 0 60
268 -70 80 40 0 0 0 - 0 0 0 0 0
~69 -80 90 10 30 0 ~0 - 0 0 0 0 0
270 -0 70 0 0 0 0 - 0 o 0 0 0
271 - 100 100 100 50 90 50 - 80 20 0 0 30
272 - 100 95 20 0 0 0 - 0 0 0 0 0
273 - 100 100 30 0 0 0 - 40 0 70 0 0
274 - 95 90 80 50 70 20 - O û 0 0 O
275 - 109 ~00 lO0 80 80 80 - 80 20 10 1~ 0
276 - ~0 0 0 0 0 0 _ o 0 0 0 0
-59-
TABLE II (Cont'd)
Compo~d Pre-emergence Post-emer~ence
Number CG FT WG _ R0 PW MD CD CG WG R0 MD_ CD_ BN
__
~77 - 99 g8 10 40 0 40 - 80 20 10 lû 30
278 - 99 96 30 0 0 0 - 70 10 0 0 50
279 - 98 98 30 0 Q 0 - 0 0 0 0 0
280 - 60 g5 20 0 0 0 - 0 0 0 0 0
281 - 95 10 0 0 0 0 - 50 0 0 0 0
282 - 20 0 0 0 0 0 - 0 0 0 0 0
2~3 - 100 100 100 100 100 100 - 90 60 100 90 100
284 - 100 100 100 100 99 99 - 90 60 80 100 30
Percent Control at 2 lbJA
Compound Pre-emerg~ CD PW Post-emer~ence
285 - 100 ~00 30 10 90 60 - 90 90 40 40 40 0
286 - 100 40 10 80 80 20 - 40 ~0 20 80 70 0
287 - lOû 100 95 95 100 100 - 9~ 70 60 75 70 100
288 - 100 100 100 85 100 100 - 75 80 75 60 7Q 0
289 - 100 100 98 80 100 100 - 60 70 50 40 75 0
~90 - 100 100 98 98 ~00 100 - 65 70 50 40 ~0 30
2~1 - lO0 100 ~OQ 95 100 lO0 - 75 75 60 30 60 0
292 - 100 100 ~00 95 100 100 - 70 75 60 60 70 50
293 - ~00 100 100 98 100 100 - 80 75 60 60 60 30
294 - 100 100 95 ~0 100 100 - 70 75 75 60 60 100
-60-
For practical use as herbicides the compounds of
this invention are generally incorporated into herbicidal
compositions which comprise an iner~ carrier and a herbici-
dally toxic amoun~ of such a compo~nd. Such herbicidal
compositions, which can also be called ormulations, enable
the ac~ive compound ~o be applied conveniently to the site
of the weed infestation in any desired q~ntity.
Useful ormula~ions of the compounds of the pre-
sent invention can be prepared in conventional ways. They
include dusts, granules, pelletsg solutions, suspe~sions,
emulsions, we~able powders~ emulsifiable concen~rates and
the like. Many of these may be applied directly. Sprayable
formulations can be extended in suitable media and used at
spray volume of from a few liters to several hundred liters
per hectare. High streng~h compositi~ns are primarily used
as intermediates for further ormulation. The ormula~ions,
broadly, contain about 1% to 99% by weight of ac~ive
ingredient(s~ and at least one o (a) about 0.1% to 20%
surfactant(s) and (b~ about 5% to 99% solid or liquid
diluent(s). More specifically, they will contain these
ingredients in the following approximate proportions:
Percent by Wei~ht
c~ive
In~redient Diluent~s~ Surfactant(s)
Wettable Powders 20-90 0-74 1-10
Oil Suspensions,
Emulsions, Solutions
(including Emulsifi-
able Concentrates) 5-50 40-95 0-15
Aqueous Suspensions10-50 40-84 1-20
Dusts 1-25 70-99 0-5
Granules and Psllets1-95 5-99 0-15
High Strength
Compositions 90-99 0-10 0-2
Lower or high levels o active ingredient can, of
course, be presen~ depending on the intended use and the
p~ysical properties o~ the compound. Higher ratios of
surfactant to active ingredient are sometimes desirable,
and are achieved by incorporation into the formulation or
by tank m~xing.
75i
Compositions including ac~ive compounds alss may
be applied by addition to irrigation waters supplied to the
field to be treated. This method of application permits
pene~ration of the compounds into the soil as the water is
absorbed therein. Compositions applied to the surface of
the soil can be incorporated and distribllted below ~he
surface of the soil b~ conventional means such as discing
or mixing operations.
The compositions can also comprise such additional
substances as other pesticides, such as insecticides,
nematocides9 fungicides, and ~he like; stabilizers, spreaders,
deactivators, adhesives, stickers, fertilizers, activators,
synergists, antidotes, and the like.
The compounds of the present invention are also
useful when combined with other herbicides and/or defoliants,
dessicants, growth inhibitors, and the like in the herbicidal
compositions heretofore described. These other materials can
comprise from about 5~/O to about 95~/O o the active ingredients
in the herbicidal compositions. Use of combinations o these
other herbicides and/or defoliants, dessicants, etc. with
the compounds of the present invention provide herbicidal
compositions which are more effective in controlling weeds
and often pro~ide results unattainable wi~h separate composi-
tions of the individual herbicides.
The other herbicides, defoliants, dessican~s and
plant growth inhibi~ors, with which the compounds of this
invention can be used in the herbicidal eompositions 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, ~,4,5-TB, 2,4,~-TES, 3,4-DA, silvex and the
like; carbamate herbicides such as IPC, CIPC~ swep, barban,
BCPC, CEPC, CPPC, and the like; thiocarbamate and dithio-
carbamate herbicides such as CDEC, metham sodium, EPTC3
diallate, PEBC, perbulate, vernolate and the like; substi-
tuted urea herbicides such as nore sifuron, dichloral
urea3 chloroxuron~ cycluron, fenuron, monuron, monuron TCA,
diuron, linuron, monolinuron neburon, buturon, trimethuron
-62-
and the like; symmetrical triazine herbicides such as
simazine, chlorazine, atraone, desmetryneg norazine3
ipazine3 prometryn, atazine, ~rietazine, simetone, prome-
tone, propazine, ametryne and the like; chloroacetamide
herbicides such as 4-(chloroacetyl)morpholine,
l-(chloroacetyl)-piperidine and the like; chlorinated
aliphatic acid herbicides such as TCA, dalapon, 2,3-di-
chloropropionic acid, 2~2g3-TPA and the like; chlorinated
benzoic acid and phenylacetic acid herbicides such as
2,3,6-TBA, 2,3,5,6-TBA, dicamba, tricamb~, amiben, fenac,
PBA, 2-methoxy-3,6-dichlorophenylacetic acid, 3-methoxy-
2,6-dlch1Orophenylacetic acid, 2-methoxy-3,5,6-trichloro-
phenylace~ic acid, 2,4-dichloro-3-nitrobenzoic acid and the
like; and such compounds as aminotriazole, maleic hydrazide,
phenyl mercuric acetate, endothal, biuret, technical
chlordane, dimethyl 2,3,5,6-tetrachloroterephthalate,
diquat~ erbon, DNC, DNBP, dichlobenil, DPA, diphenamide,
dipropalin, trifluralin, solan, dicryl, merphos, DMPA, DSMA,
MS~A, pottasium azide, acrolein, benefin, bensulide, AMS,
bromacil, 2-(3,4-dichlorophenyl)-4-methyl-1,2,4-oxazolidine-
3,5-dione, bromoxynil, cacodylic acid, CMA, CPMF, cypromid,
DCB, DCPA, dichlone, diphenatril, DMTT~ DNAP, EBEP, EXD,
HGA, ioxynil, IPX, isocil, potassium cyanate, MAA, MAMA~
MCPES, MCPP, MH, molinate, NPA, OCH, paraquat, PCP, picloram,
DPA, PCA, pyrichlor, sesone, terbacil, terbutol, TCBA,
brominil, CP-50144, H-176-1, H-732, M-Z901, planavin, sodium
tetraborate, calcium cyanamid, DEF, e~hyl xanthogen disul-
fide, sindone, sindone ~, propanil and the like.
Such herbicides can also be used in the methods
and compositions of this invention in the form o their
salts, esters, amides, and other derivatives whenever
applicable to the particular parent compounds.
Weeds are undesirable plants growing where they
are not wanted, having no relative economic value, and
interfering wi~h the produc~ion of cul~ivated crops, with
the growing of ornamental plants, or with the welfare of
li~estock.
-63-
Similarly, such weeds can be classified as broad-
leaf or grassy weeds. It is economically desirable to
control the growth o~ such weeds without damaging beneficial
plants or livestock.
