Note: Descriptions are shown in the official language in which they were submitted.
~;~7~L~4~
61936-1715
--1--
Z-[1-(3-CHLOROALLY~OXYAMINO) ALKYLIDENE]-5-
ALKYLTHIOALKYL-CYCLOHEXANE-1,3-~IONE EERBICIDES
BACKGROUND OF-THE INVENTION
This invention relates to certain trans 2-11-(3-
chloroallyloxyamino) propylidene~-5-(alkylthioalkyl)cyclo-
hexane-1,3-dione and salts thereo~ and to the use of such
compounds as herbicides.
U.S. Patent No. 4,440,566, issued April 3, 1984,
discloses compounds having the formula:
\C~
() q/q, oR 5
~2 R3 ~X)
wherein R is most preferably alkyl of 1 to 3 carbon
atoms, most pre~erably ethyl or propyl;
Rl is most preferably 3-trans-chloroallyl or 4-chlo-
robenzyl;
R2 and R3 are preferably each alkyl o 1 to 3 carbon
atoms or one of R2 or R3 is hydrogen and the other i5
alkylthioalkyl having 2 through 8 carbon atoms, ~ost pre~
ferably R2 and R3 are each methyl or one of R2 or R3 is
hydrogen and the other is 2-ethylthiopropyl.
This patent also teaches that these compounds
exhibit herbicidal activity against grasses and are sa~e
with respect to broad-leaf crops.
SUMMARY OF THE INVENTION
I~ is has now been discovered that certain o~
~0 the compounds (i.e., see Formula I below) encompassed
within U.S. Patent No. 4,440,566, exhiblt surprisingly
.,
.
~L2'7~L644
~1 -2-
~ superior herbicidal activity as compared with others.
; Although, the compounds encompassed within Formula (X)
05 above, generally exhibit very good herbicidal activity,
the outstanding herbicidal activity possessed by the
present compounds rarely exists and cannot be predicted
beforehand.
The present compounds exhibit both pre-emergence
and post-emergence phytotoxicity with respect to grasses
and exhibit excellent especially post-emergence herbicidal
activity against Bermudagrass, foxtail, crabgrass, volun-
teer corn, volunteer sorghum, barnyardgrass, broad-leaf
signalgrass, goosegrass, red rice, sprangletop, seedling
Johnsongrass and Rhizome Johnsongrass.
The compounds of Formula I exhibit excellent
phytotoxicity against grasses at even very low application
rates and may be safely applied with respect to broad-leaf
crops at such rates. Thus, the present compounds are
~U especially useful for controlling grassy weeds in broad-
leaf crops and are especially useful to control grassy
weeds in soybean crops.
The compound of the present invention can be
represented by the following formula:
NOR
C~
CH3CH~
O ~ - OH
~ ~
~; /\
H R2
(I)
wherein Rl is 3-trans-chloroallyl and R2 is 2-methyl-
thiopropyl or 2-propylthioethyl.
The invention also comprises compatible salts of
the compound of Formula I.
~0
~27~64~
~1 -3-
As is well recognized, compounds of the nature
of Formula (I) exist as tautomers~ The compounds also
have two asymmetric carbon atoms and can also exist as
optical isomers. The above formula is intended to encom-
pass the respective tautomeric forms as well as the indi-
vidual optical isomers as well as mixtures thereof and the
respective tautomers and optical isomers as well as mix-
tures thereof are encompassed within the invention~
In a further aspect the invention provides aherbicidal composition comprisin~ a compatible carrier and
a herbicidally effective amount of the compound(s) of the
invention or mixtures thereof.
The present invention also provides a method for
preventing or controlling the growth of unwanted grassy
vegetation, which comprises treating the growth medium
and/or the foliage of such vegetation with a herbicidally
effective amount of the compound(s) of the invention or
~U mixtures thereof.
The present invention also provides a method for
regulating plant growth which comprises treating the
growth medium and/or the foliage of such vegetation with a
plant growth reyulating effective amount of the com-
pound(s) of the invention or mixtures thereof, effectiveto alter the normal growth pattern of said plants.
The present invention also provides chemical
intermediates and processes for preparing the compounds of
the invention.
The invention will be further described herein-
below.
FURTHER DESCRIPTION OF THE
INVENTION AND THE PREFERRED EMBODIMENTS
The compound of Formula (I) can be conveniently
prepared by the following schematically represented pro-
cess:
.,
~.~7~4~
01 -4-
CH3CH2 ~
05
O ~ OH
~J + H2NORl >
~ lB)
H R
(A)
wherein ~1 and R2 are as defined hereinabove.
This process can be conveniently effected by
contacting Compound (A) with 3-trans-chloroallyloxyamine
(B), preferably in an inert organic solvent.
Typically, this process is conducted at tempera-
tures in the range of about from 0 to 80C, preferably
about from 20 to 40C, for about from 1 to 48 hours, pre-
ferably about from 4 to 12 hours, using about from 1 to 2,
preferably 1.05 to 1.2 moles of 3-trans-chloroallyloxy-
amine ~B) per mole of Compound (A). Suitable inert
organic solvents which can be used include, for example,
lower alkanols, e.g., methanol, ethanol, ethers, e.g.,
ethyl ether; methylene chloride. Two-phase water and
immiscible organic solvent (e.g., hexane), and mixtures
thereof can also be used as the reaction medium.
Trans-chloroallyloxyamine is a known compound
and can be prepared via known procedures, such as, for
example, described in V~S. Patent No. 4,440,566. The
trans-chloroallyloxyamine reactant can be provided by
neutralizing a hydrochloride salt of trans-chloroallyloxy-
amine in situ with an alkali metal alkoxide.
The starting materials of Formula (A) can also
be prepared via the general procedure described in U.S.
Patent No. 4,440,566.
The compatible salts of Formula (I) can be pre-
pared by conventional procedures, for example, via the
reaction of the compound of Formula I with a base, such
as, for example, sodium hydroxide, potassium hyclroxide and
~L~716~
Ol _5_
the like, having the desired cation. Additional varia-
tions in the salt cation can also be effected via ion
05 exchange with an ion exchange resin having the desired
cation.
General Process Conditions
The reaction product can be recovered from its
reaction product mixture by any suitable separation and
purification procedure, such as, for example~ chromato-
graphy. Suitable separation and purification procedures
are, for example, illustrated in the Examples set forth
hereinbelow,
Generally, the reactlons described above are
conducted as liquid phase reaction and hence pressure is
generally not significant except as it affects temperature
(boiling point) where reactions are conducted at reflux.
Therefore, these reactions are generally conducted at
pressures of about from 300 to 3,000 mm of mercury and
~V conveniently are conducted at about atmospheric or ambient
pressure.
It should also be appreciated that where typical
or preferred process conditions (e.g., reaction tempera-
tures, times, mole ratios of reactants, solvents, etc.)
have been given, that other process conditions could a~so
be used. Optimum reaction conditions (e.g., temperature,
reaction time, mol ratios, solvents, etc.) may vary with
the particular reagents or organic solvents used but can
be determined by routine optimization procedures.
Where optical isomer mixtures are obtained, the
respective optical isomers can be obtained by conventional
resolution procedures. Geometric isomers can be separated
by conventional separation procedures which depend upon
differences in physical properties between the geometric
isomers. ~owever, it is generally preferable to use the
desired isomeric starting material in the reaction.
Definitions
_
As used herein the following terms have the
following meanings unless expressly stated to the
contrary:
1~716~
01 -6-
The term "2-methylthiopropyl" refers to the
group having the formula:
05
IH3
-CH2--CH-S-CH3-
The term "2-propylthioethyl" refers to the group
having the formula -cH2-cH2-s-cH2cH2cH3~
The term "compatible salts" refers to salts
which do not significantly adversely alter the herbicidal
properties of the parent compound. Suitable salts include
cation salts such as, for example, the cation salts of
lithium, sodium, potassium, alkali earth metals, copper,
zinc, ammonia, quaternary ammonium salts, and the like.
The term "room temperature" or "ambient tempera-
ture" refers to about 20-25C.
Utility
~0 The compounds of Formula (I) and their salts
exhibit both pre- and post-emergent herbicidal activity
and exhibit especially good herbicidal activity against
grasses. The compounds exhibit especially good phyto-
toxicity against foxtail, Bermudagrass, crabgrass,
rhizone, Johnsongrass and volunteer corn. These weed
species are generally very diEficult to control and hence,
the present compounds provide a significant advantage
which respect to the control of such weeds.
Generally, for post-emergent applications, the
herbicidal compounds~are applied directly to the foliage
~ or other plant parts. For pre-emergence applications, the
^~ herbicidal compounds are applied to the-growth medium, or
prospective growth medium, for the plant. The optimum
amount of the herbicidal compound or composition will vary
with the particular plant species, and the extent of plant
growth, if any, and the particular part of the plant which
is contacted and the extent of contact. The optimum
dosage can also vary with the general location, or
environment (e.g., shelte~ed areas such as greenhouses
compared to exposed areas such as Eields), and type and
ol -7-
degree of control desired. Generally, for both pre- and
post-emergent control, the present compounds are applied
at rates of about from 0.02 to 60 kg/ha, preferably about
from 0.02 to 10 kg/ha.
Also, although in theory the compounds can be
applied undiluted, in actual practice they are generally
applied as a composition or formulation comprising an
effective amount of the compound(s) and an acceptable car-
rier. An acceptable or compatible carrier (a~riculturally
acceptable carrier) is one which does not significantly
adversely affect the desired biolog~cal ef~ect achieved by
the active compounds, save to dilute it. Typically, the
composition contains about ~rom 0.05 to 95% by weight of
the compound of Formula (I) or mixtures thereof. Concen-
trates can also be made having high concentrations
designed for dilution p-ior to application. The carrier
can be a solid, liquid, or aerosol. The actual composi-
tions can take the form of granules, powders, dusts, solu-
tions, emulsions, slurries, aerosols, and the like.
Suitable solid carriers which can be used
include, for example, natural clays (such as kaolin, atta
pulgite, montmorillonite, etc.), talcs, pyrophyllite,
diatomaceous silica, synthetic fine silica, calcium alumi-
nosilicate, tricalcium phosphate, and the like. Also,
organic materials, such as, for example, walnut shell
flour, cotton-seed hulls, wheat flour, wood flour, wood
bark flour, and the like can also be used as carriers.
Suitable liquid diluents which can be used include, for
example, water, organic solvents (e.g., hydrocarbons such
as benzene, toluene, dimethylsulfoxide, kerosene, diesel
fuel, fuel oil, petroleum naphtha, etc.), and the like.
Suitable aerosol carriers which can be used include con-
3~ ventional aerosol carriers such as halogenated al~anes,etc.
The composition can also contain various promo-
ters and surface-active agents which enhance the rate of
transport of the active compound into the plant tissue
4~ such as, for example, organic solvents, wetting agents and
01 -8-
oils, and in the case of compositions designed for pre-
emergence application agents which reduce the leachability
05 of the compound or otherwise enhance soil stability. Crop
oils, such as, for example, soybean oils, paraffin oils
and olefinic oils, are especially advantageous as carriers
or additives in that they enhance phytotoxicity.
The composition can also contain various com-
patible adjuvants, stabilizers, conditioners, insecti-
cides, fungicides, and if desired, other herbicidally
active compounds.
One convenient concentrate formulation which can
be used comprises 23-27% by weight of the active herbicide
of the invention, 2 to 4% by weight of an emulsifier, for
example, calcium alkylbenzene sulfonates, octylphenol-
ethoxylate, etc., or mixtures thereof, and about 70~75~
organic solvent, for example, xylene, etc. The concen-
trate is mixed with water and preferably a crop oil prior
to application and applied as a water emulsion containing
~; about 0.5 to 2~ of a crop oil, for example, soybean oils,
and paraffinic oils and olefinic oils. Conveniently, the
herbicide is applied as water emulsion containing about
0.02-0.6 wt. %, preferably 0.07-0~15 wt. ~ of the herbi-
cide, of the invention; about 0~001-0.01 wt. % of an emul-
sifier; about 0.08-2.5 wt. % of an organic solvent and
about 95 to 99 wt. % water. Preferably, the composition
, also contains about 0.25 to 2 wt. % of a crop oil. The
application composition can be conveniently prepared by
mixing the concentrate formulation with about 1/4 to 1/2
the desired amount of water. Then admixing the crop oil
; and then adding the remaining amount of water. IE no crop
oil is used, then the water and concentrate formulation
are simply admixed together.
3~ A further understanding of the invention can be
had in the following non-limitin~ Preparation(s) and
Example(sl. Wherein, unless expressly stated to the con-
trary, all temperatures and temperature ranges refer to
the Centigrade system and the term "ambient" or "room
temperature" refers to about 20-25C. The term "percent"
or "~" refers to weight percent and the term "mole" or
"moles" refers to gram moles. The term "equivalent"
refers to a quantity of reagent equal in moles, to the
moles of the preceding or succeeding reactant recited in
that example in terms of finite moles or finite weight or
vo~ume. Where given, proton-magnetic resonance spectrum
(p.m.r. or NMR) were determined at &0 mHz, signals are
assigned as singlets (s), broad singlets (bs), doublets
(d), double doublets (dd), triplets (t), double triplets
(dt), quartets (q), and multiplets (m); and cps refers to
cycles per second. Also where necessary examples are
repeated to provide additional starting material for sub-
sequent examples.
EXA~PLES
Example 1
Trans-2-[1-(3-chloroallyloxyamino) propylidene]~5-
(2-methylthiopropyl)-cyclohexane-1,3-dione
(a) To a cooled solution containing 48 g
(1.0 mole) of methylmercaptan in 250 ml of methylene chlo-
ride was added 82.4 g of crotonaldehyde solution, contain-
ing 15~ water 85% crotonaldehyde (1.0 mole) followed by
the addition of 2 ml of triethylene amine. The resulting
exothermic reaction caused the mixture to reflux for about
2 minutes. The mixture was stirred at room temperature
overnight (aoout 18 hours) and then dried over magnesium
sulfate and filtered. The filtrate was concentrated by
evaporation affording a 142.4 g of concentrate containing
78 wt. ~ beta-methylthiobutyraldehyde and 22~ methylene
chloride,
(b) 71.2 Grams (0.5 mole) of beta-methylthio-
butyraldehyde was dissolved in 500 ml of methylene
chloride. 159.18 Grams ~0.5 mole) of triphenylphosphor-
anylidene 2-propanone was then added and the mixture
stirred at room temperature overnight (about 18 hours~.
The methylene chloride was evaporated off leaving a solid
residue. ~he residue was slurried in hexane, filtered.
The remaining solids were thoroughly washed with hexane
and filtered. The combined filtrates were evaporated to
~1~44
61936-1715
--10--
dryness affording 70.6 g of 6-me~hylthio-3-hepten-2-one as
an oil. (For large scale operations this product can also
05 be conveniently prepared by the general procedures
described in U.S. Pa~ent No. 4,35~,184 and PCT/US 85/
01853, published April 10, 1986 as WO 86/02065.
I0 (c~ 66.0 Grams (0.5 mole~ of dimethyl malonate
was added dropwise to a solution cont~ining 27 9 ~0.5
mole3 of sodium methoxide in about 300 ml of methanol at
0-5C followed by the dropwise addition 79.5 9 (0.5 mole)
of 6-methylthio-3-hepten-2-one. The temperature of the
mixture was allowed to rise to room temperature. The
mixture was stirred overnight (about 18 hours) at room
temperature. The mixture was evaporated to dryness and
the residue mixed wlth 300 ml of water. The re~ulting
aqueous solution w~s washed with ethyl ether, then acidi~
fied with concentrated hydrochlorlc acid to pH2 and
extracted with methylene chloride. The methylene chloride
extract was dried over magnesium sulfate and evaporated to
dryness affording 4-methoxycarbonyl-5-(2-methylthiopropyl)-
cyclohexane 1,3-dione.
(d) A mixture containing 129 g (0.5 mole) of 4-
methoxycarbonyl-5-(2-methylthiopropyl)-cyclohexane-1,3-
dione and 65 g of aqueous 85 wt.% potassium hydroxide
(1 mole) in 300 ml of ethanol was refluxed for 2 hours and
then stirred overnight (about 18 hours) at room tempera-
ture. The mixture was evaporated to dryness and the resi-
due dlssolved in water. The resulting aqueous solution
was washed with 100 ml of ethyl ether, then acidified to
pHl with 6N aqueous hydrochloric acid and extracted twice
with methylene chloride. The combined methylene chloride
extract was washed with water, dried over magnesium sul-
fate and evaporated to dryness affording 60 9 of 5-(2-
methylthiopropyl) cyclohexane-1,3-dione as an oil which
solidieied upon standing for 3 or 4 days.
(e) 8.8 Grams ~0.088 mole) of trlethylamine was
slowly added over a five-minute period to a mixture
. .
6~
~
containing 16.0 g (0.08 mole) of 5-(methylthiopropyl)cyclo-
hexane-1,3-dione in 200 ml of toluene after which 2.4 g
05 (0.02 mole) of dimethylaminopyridine was added. 7.7 Grams
(0.084 mole) of propionyl chloride was added dropwise to
this mixture over a 20-minute period. The mixture was
maintained at 65-70C for 3 hours and then cooled to room
temperature and allowed to stand overnight (about 18
hours). The mixture was washed first with water and then
with aqueous 10 wt. % hydrochloric acid. The resulting
aqueous and toluene liquid phase layers were then
separated. The aqueous layer was extracted with toluene
and the axtract combined with the previously separated
toluene layer. The toluene phase was extracted with
aqueous 1 wt. ~ sodium hydroxide. The extract was washed
~ with methylene chloride, then acidified to pHl with hydro-
; chloric acid, and extracted with methylene chloride. The
methylene chloride extract was dried over magnesium sulfate
and evaporated to dryness affording 2-propionyl-5-t2-methyl-
thiopropyl)cyclohexane-1,3-dione.
(f) A solution containing 4.2 g (0.0117 mole)
of 2~propionyl-5-(2-methylthiopropyl)cyclohexane-1,3-dione
and 2.7 9 of 3-trans-chloroallyloxyamine in 50 ml of
ethanol was stirred at room temperature over the weekend
(about 2-1/2 days) and then evaporated to dryness. The
residue was dissolved in methylene chloride and extracted
twice with aqueous 1 wt. % sodium hydroxide. The aqueous
extract was washed with ethyl ether, then acidified to pHl
with hydrochloric acid and then extracted with methylene
chloride. The methylene chloride extract was dried over
magnesium sulfate and then evaporates to dryness affording
2.1 9 of the title compound as an oil.
Elemental analysis Carbon: calc. 55.56%, found
55.96~; Hydrogen: calc. 6.99~, found 7.32%; Nitrogen
calc. 4.05 %, found 4.2~.
qO
-12-
01
Example 2
2-[1-(3-trans-chloroallyloxyaminc))propylidene]-
5-(2-propylthioethyl)-cyclohexane-1,3-dione _
05 A 42.3 wt.% solution of the hydrochloride salt
of trans-chloroallyloxyamine in dilute aqueous hydrochlo-
ric acid solution was treated with dilute aqueous sodium
hydroxide to pH 8-10 to liberate the free amine. The
solution was then extracted twice with ethyl ether. The
~ ether extracts were combined, washed twice with saturated
aqueous sodium chloride and then driad over magnesium
sulfate and evaporated yielding chloroallyloxyamine as a
pale yellow liquid.
A mixture containing 3.2g of 2-propionyl-S-(2-
IS propylthioethyl)cyclohexane-1,3-dione and 1.3g or trans-
chloroallyloxyamine in 20 ml of ethanol was stirred over-
night (about 15-18 hrs.) at room temperature and then
concentrated by evaporation and mixed with 50 ml of ethyl
ether. The pH of the mixture was adjusted to pH 11-12 by
the addition of aqueous 5 wt. % sodium hydroxide. The
aqueous phase was separated and treated with aqueous 10
wt.% hydrochloric acid to pH 2 and then extracted twice
with ethyl ether. The ethyl ether extracts were combined,
washed twice with aqueous sodium chloride, dried over
magnesium sulfate and concentrated by evaporation to a
yel;low liquid. The yellow liquid was chromatographed
through a silica gel column eluting with methylene chlo-
ride affording 3.1 g of the title compound as an oil.
Example 3
Trans-2-[1-(3-chloroallyloxyamino) propylidene]-5-
(2-ethylthiopropyl)-cyclohexane-1,3-dione
In this example, 17.2 g (0.0636 mol) of 2-pro-
; pionyl-5-(2-ethylthiopropyl)cyclohexane-1,3-dione; 0.9 g
(0.0153 mol) of acetic acid, and 10.9 g (0.0757 mol) of
3S 3-trans-chloroallyloxyamine in 35 ml of water were added
to 20 ml of hexane and stirred. Agueous 5 wt. ~ sodium
hydroxide was slowly added over about 15 minutes until 3.0
g (0.0757 m ~ small excess) of sodium hydroxide had been
added - pH of reaction mixture about 6. The mixture was
heated to and maintained at 40C for 2-1/2 hours and then
-13-
01
cooled to room temperature. The or~anic (i.e., hexane)
phase was separated and washed with 10 ml of aqueous
05 5 wt % hydrochloric acid and then aqueous 6.25 wt. %
sodium hydroxide added until pH12. The aqueous phase was
separated and admixed with 25 ml of hexane and the pH
adjusted to 5.4 by the dropwise addition of aqueous
36 wt. ~ hydrochloric acid over an ice bath. The organic
phase was separated, dried over magnesium sulfate and then
concentrated by evaporation affording 18.0 ~ of a crude
product. The crude product was purified by column chroma-
tography over silica gel eluting with hexane:methylene
chloride affording the purified title compound as an oil.
IS Elemental analysis carbon calculated 56.73~, found 56.63~;
Hydrogen calculated 7.28%, found 7.55~; Nitrogen 3.89%,
found 3.55%.
Example 4
Sodium 2-~1-(3-trans-chloroallyloxyamino)
propylidene-3-oxo-5-(2-methylthiopropyl)-
~U _ cyclohex-l-en-l-olate
This example illustrates a procedure which can
be used to prepare the title compound.
A solution containing 0.01 mole of sodium
hydroxide dissolved in 2 ml of water is added to a solu-
tion containing 0.01 mole of 2-~1-(3-trans-chloroallyl-
oxyamino~ propylidene-5-(2-ethylthiopropyl)-cyclohexane
1,3-dione at room temperature. After the reaction is
completed, the solvents are evaporated off under vacuum
affording the l-hydroxy sodium salt of 2-[1-(3-trans-chlo-
roallyloxyamino) propylidene-3-oxo-5-(2-methylthiopropyl)-
cyclohex-l-en-l-ol,
Example 5
In this example, the title compound of Examples
1-3, i.e., 2-~1-(3-trans-chloroallyloxyamino)
propylidene]-5-(2-~ethylthiopropyl)-cyclohexane-1,3-dione
(1); 2-[1-(3-trans-chloroallyloxyamino) propylideneJ-5-(2-
propylthioethyl)-cyclohexane-1,3-dione (2~;and 2-11-(3-
trans-chloroallyloxyamino)propylidene]-5-(2-ethylthio-
propyl) cyclohexane-1,3-dione (3); were tested, u~ing the
procedures described hereinbelow, for pre-emergent and
~27~L6~
01 -14-
post-emergent phytotoxic activity against a variety of
grasses and broad-leaf plants including one grain crop and
one broad-leaf crop.
Pre-Emergent Herbicide Test
Pre-emergence herbicidal activity was determined
in the following manner.
Test solutions of the respective compounds were
prepared as follows:
355.5 mg of test compound was dissolved in 15 ml
of acetone. 2 ml of acetone containing 110 mg o~ a non-
ionic surfactant was added to the solution. 12 ml o~ this
stock solution was then added to 47.7 ml of water which
contained the same nonionic surfactant at a concentration
of 625 mg/l.
Seeds of the test vegetation were planted in a
pot of soil and the test solution was sprayed uniformly
onto the soil surface at a test compound dose of
27.5 micrograms/cm2 unless otherwise specified in the
following Tables. The pot was watered and placed in a
greenhouse. The pot was watered intermittently and
observed for seedling emergence, health of emerging seed-
lings, etc., for a 3-week period. At the end of this
period, the herbicidal effectiveness of the compound was
rated based on the physiological observations. A 0-to-100
scale was used, 0 representing no phytotoxicity, 100
t; representing complete kill. The results of these tests
are summarized in Table 1.
Post-Emergent Herbicidal Test
The test compound was formulated in the same
manner as described above for the pre-emergent test.
This formulation was uniformly sprayed on 2 similar pots
containing plants 2 to 3 inches tall (except wild oats,
soybean and watergrass which were 3 to 4 inches tall)
(approximately 15 to 25 plants per pot) at a test compound
dose of 27.5 microgram/cm2 unless otherwise specified in
the following Tables~ After the plants had dried, they
were placed in a ~reenhouse and then watered intermit-
tently at their bases as needed. The plants were observed
~L~7.~ E;`~
01 -15-
periodically for phytotoxic effects and physiological and
morphological responses to the treatment. After 3 weeks,
05 the herbicidal effectiveness of the cornpound was rated
based on these observations. A O-to-100 scale was used,
O representing no phytotoxicity, 100 representing complete
kill. The results of these tests are summarized in
Table 2.
.~
~ o o o
~) o o o
.
a~
o o o o
O u 3 ooo
~ U~ X
O u)
V ~ o o o
c ~ n o o o
,~ u7 ro
~ c ~u) ooo
~ ~ o, ~ ~
e ~1 0 0 0
U ~
~ ~I C :~ ,~ o o In
~ ~ u o ~1 o o o
~ O ~ ~
3 .c
m
.~ ~ ~
. ~ e
o O ~,
eæ
o c ~ o
` ~71~i4~
t,l o o o
. I
~1
ol O O O
O
~, ~,
o X
3 ~7 D ~ o O O
~ O ~ t~
D ~
e ~ ~ ~
~ ~n ~ o o O
1~ ~ ~: ~ 3 d~ 'r
l ~ ~ P-
O ~ ~ U ~
1~ v as Ln o u~)
c ~ O 5~ ~r ~ d' !
00"
O
Q. O
~ ~;
C~ ~ O
6~
l -18-
Example 6
In this example, the title compounds of Examples
05 1-3 were tested for post-emergence herbicidal activity at
very low dosage rates side by side with trans-2-[1-(3-
chloroallyloxyamino)butylidene]-5-(2-ethylthiopropyl)-
cyclohexane-1,3-dione ("C-l") the commercial herbicide
Sethoxydim ("C-2") (i.e., 2-[1-~ethoxyamino)butylidene]-5-
10 (2-ethylthiopropyl)-cyclohexane-1,3-dione against an
expanded list of weed grasses and two crops.
The tests were conducted in the same manner as
described in Example 5, hereinabove, with the exception
that the dosages indicated in Table 3 were used and four
l5 replicates were used per test. The results of this
r testing are summarized in Table 4 wherein O indicates no
phytotoxicity and 100 indicates complete kill. Generally,
phytotoxicities below about 20-30% are not considered
meaningful because generally the plant can grow out of
this amount of injury.
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s a o o o o o o o o o o o o
d~ O
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~ 3~ 0 0 0 o O
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Ol -21-
As can be seen from Table 3, all of the com-
pounds were inactive against yellow nutsedge at these
S dosage rates. With this one exception, Compounds 1-3 were
superior to Compound C-l with respect to each of the other
weed species in the test and were greatly superior to
Compound C-2.
In terms of dosages required to evoke equivalent
responses, an application rate of Compound 1 or 2 of 0.05
y/cm2 was about equivalent or superior to an application
rate of Compound C-l of 0.28 y/cm2 to control crabgrass
and Johnsongrass. An application rate of 0.05 y/cm2 of
Compound 1 or 2 was equivalent to an application rate of
0.11 y/cm2 of Compound C-l to control barnyardgrass. With
respect to wild oats and yellow foxtail, an application
rate of 0.11 y/cm2 of Compound 1 or 2 provided superior
control over application rate of 0.28 y/cm2 of Compound
C-l. As above noted, Compound C-l was superior to
Compound C-2 and the dosages advantages afforded by
Compounds 1 and 2 were even greater with respect to
Compound C-2.
Obviously, ~any modifications and variations of
the invention described hereinabove and below can be made
without departing from the essence and scope thereof.
3~
