Note: Descriptions are shown in the official language in which they were submitted.
~37~
PR-5693/5694/6175/6510
Field of the Invention
m is invention relates to antidotes for pyrrolidone herbicides,
and, more particularly to the fsllowing four antidotes: N-ethyl-N-~enzyl-
dichloroacetamide; N,N-diallyldichloroacetamide;
and 2,2,2-trifluor oe thyl~N~p~chlorophenylcarba-
mate~
An herbicide is a oompound which cDntrols or mLdifies plant
groMth, e.g., kill~n~, retarding, defoliatinq, desiccating, regulating,
stunting, tillering, stLmulating, and dwarfing. The term "plant" refers
to all physical parts of a plant, including seeds, seedlings, saplings,
roots, tubers, stems, stalks, foliage, and fruits~ "Plant growth"
includes all phases of develoFment from se~ germination to natural cr
induced cessation of life.
Herbicides are generally used to oontrol or eradicate w~ed
pests. Ihey have gained a high degree o~ mnercial success becau æ it
has been shown that such control can increase crop yield and reduce hæ -
vesting costs.
~ he most popular methods of herbicid~ application include: pre-
plant incorporation into the ~il; in-furrow application to seeds and sur-
rounding soil pre-emergence surface treatment of seeded soil; and post-
emergen oe treatm~nt of the plant and soil.
A manufacturer cf an herbicide generally recommends a range ofapplication rates and concentrations calculated to maximize weed control.
The range of rates v2ries frcm approx~nately 0,01 to 50 pounds per acre
(000112 to 56 kilogra~ per hectare (k/ha))~ and is usually in the range
oE from 0.1 to 25 pounds per acre (0.112 to 28 k/ha). Ihe term "herbici-
dally effective a~ount" describes ~he amount of an herbicide oo~pound
which oontrols or modifies plant growth. Ihe actual amount used depends
,~
~3~
upon several considerations, including particular weed susceptibility and
overall cost limitations.
m e most important factor influencing the usefulness of a given
herbicide is its selectivity towards crops. In some cases, a beneficial
crop is susceptible to the effects of the herbicide. In additionr cer-
tain herbicidal compounds are phytotoxic to some weed species but not to
others. To be effective, an herbicide must cause minim~l damage (prefer-
ably n~ damage) to the beneficial crop while maximizing damage to weed
species which plague that crop.
Depending on the particL~ar formulation used, the pyrrolidone
herbicide compounds of this invention have either of t~ different effects
on crops and weeds. ~hen a pyrrolidone compound is formulated as an emul-
sifiable concentrate and applied, bleaching of the crcp occurs in the
early stages of ~rowth~ Bleaching is due to loss of pigmentation in a
plant and is seen as a yellowing of the plant's leaves.
When a pyrrolidone compound is fa,rmulated as a microcapsule,
bleaching of the crop is significantly lessened. However, weed control
is also reduced.
Tb preserve the beneEicial aspects of herbicide use, i.e~, to
maximize weed control, and to minimize cra~ damage, many herbicide anti-
dotes have been prepared. Ihese antidotes reduce or el~ninate damaqe ~o
the crop while maintaininq or increasing the damaging effect of the herb-
icide on weed species; See, for example, U.SO Patent Nos. 3,959,304;
4,021,224 and 4,021,229 and Belgian Patent ~o. 846,894.
The precise mechanism by which an antidote reduces herbicidal
crop injury has not been established. An antidote oompound may be a
remedy, interferent, protectant, or anta~onist~ As used herein, "anti-
dote" describes a compound which has the effect of establishing herbicide
selectivity~ i.e., continued herbicidal phytotoxicity to weed species and
reduced or non-phytotoxicity to cultivated crop species. The term "anti~
dotally effective amount" describes the amount of an antidote oompound
~37~
which counteracts a phytotoxic response of a beneficial crcp to an herbi~
cide~
Description of the Invention
Ihe following o~mp~unds ha~e now been discovered to be effective
antidote~s for pyrroliZone herbicide in~ury to a wide variety of crops:
1. ~-e~hyl~N-benzyldichloroacetamide having the formula
~ C2H5
Cl2CHC-N
\ CH ~
2. 2t2,2-trifluoroethyl-~-p-chlorophenylcarbamate ha~ing ~he
formula
Cl~NEllCI OCH2CF3
and
3. N,N-diallyl-dichlorvacetamude havinq the formula
Cl 11 ~ ~12-CH=CH~
H- IC~C-N
Cl \ CH2-CH=CH2
m~S invention embodies a two-part herbicidal system ccmprising:
(a) an herbicidally effective amount of a Fyrrolidone corpound
of the formula
~. ~
3~
X O
H I~-C~'2/
R2 H
irl which
X is hy~rogen, chlorine or methyl;
Y is hydrogen, chlorine or bromine;
Z is chlorine or bromine;
R is hydro~en, alkyl having 1 to 4 carbon atoms, inclusive,
acetyl, ohlorine, brcmune, fluorine~ iodine, trifluoromethyl, nitro,
oyano, alkoxy having 1 to 4 carbcn atom~, inclusive, alkylthio having 1 to
4 carbon atoms, inclusive, alkylsulfinyl having 1 to 4 carbon atoms, in-
clusive, alkylsulfonyl having 1 to 4 carbon atoms, inclusive, trifluoro-
methylthio, trifluorcmethylsulfinyl, trifluoromethylsulfonyl, Fentafluoro-
propionamido, or 3-methylureido;
Rl is hydroqen, alkyl having 1 to 4 carbon atans, inclusive,
chlorine or trifluo~omethyl; and,
R2 is alkyl having 1 to 4 carbon atons, inclusive, or hydrogen;
and,
(b) a non-phytotoxic antidotally effective amount of a oompound
having one ~f the following f~rmulas:
/ C2H5
l(b) C12C~C-N
\ CH2~3
2(b) Cl- ~ OCH2CF3 ; or
I1 ~ / CH2-cH=cH2
3tb) H ~ ~-C-N\
Cl CH2-CH-~H2
, ,, .. ,. - - - : ~
In a preferred embcdiment, X i.s hydrogen, Y is chlorine, Z is
chlorine, R is m-trifluoromethyl, Rl is hy~rogen and R2 is hydrogen.
This inven~ion also includes the method o~ controlling undesir-
able vegetation and at the same time reducinq herbicidal crop injury due
to a pyrrolidone herbicide which ~om~rises applying to the locus where
control is desixed a composition oo~prisin~:
(a) an herbicidally effective amount of a pyrrolidone compound
of the fo~nula
X O
Z ~H - ~ 2/ ~ ~l
R2 H
in which
X is hydrogen, chlorine or methyl;
Y is hydrogen, chlorine or bromine;
Z is chlorine or bran.ine;
R is h~ldrogen, alkyl having 1 to 4 carbon atoms, inclusive,
acetyl, chlorine, bromine, fluorine, iodine, trifluoromethyl, nitro,
cyano, alkoxy having 1 to 4 carbon atoms, inclusive, alkylthio having 1 to
4 carbon atoms, inclusive, alkylsulEinyl havin~ 1 to 4 carbGn atoms, in-
clusive~ alkylsulfonyl having 1 to 4 carkon atoms, inclusive, trifluoro-
methylthio, trifluoromethylsulfinyl, trifluoromethylsulfonyl, pentafluoro-
propion~nido, or 3-methylureidos
Rl is hydrogen, alkyl having 1 to 4 carbon atoms, inclusivet
chlorine or trifluoromethyl; and,
R2 is alkyl having 1 to 4 carbon atoms, inclusivem or hydroqen;
and,
(b) a non phytotoxic antidotally effective amount of a oompo-md
having one of the following formulas:
Il / C2H5
1(b) C12~C-N
\ CH2~)
2(b) Cl- ~ lCOC~2CF3 , or
Cl jl ~ CH2-CH=CH2
3(b) H-C~-C~N
Cl CH2-CH-CH2
r~he locus where herbicidal s21ectivity iS desired may include
soil, seedq, seedlings and vegetation.
Preparation
rLhe pyrrolidone compounds of the present inventior. can be pre-
pared by the procedures described in U.S. Patent ~o. 4,110,105.
r~he N-ethyl-N-benzyldichloroacetamide compound of this invention
may be prepared accordiny to the followin~ procedure. Fourteen and two-
tenths ~rams ~14.2 g~ (0.105 mole) of N-ethylamine, 4.0 ~ (0.1 mole) of
sodium hydroxide, 50 milliliters (ml) of water and 100 ml oE methylene
chloride were added to a reaction flask. Fourteen and seven-tenths g of
2~2-dihloroacetyl chloride were added dr6pwise with dry ice coolin~ cver
a period of 3 minutes. ~boling was rem wed and the mixture was stirred
for an additional 18 minutes.
The reaction mixture was separated and the organic phase was
washed twi oe with dilute h~drochloric acid, twice with 5~ sodium carbon-
ate~ dried over magnesium sulfate and stripped over water pump vacuum toyield 21~9 g of 2,2-dichlo~o-M-ethyl-N-benzylacetamide (residual liquid).
~D30 = 1.5449. Structure was oonfirmed by infrared spectrosopy.
~ he trifluoromethyl p-chlorophenylc~rbamate ooTpound of this
i~vention m~y be prepared according to the following procedure~
Two and one-half qrams (2.5 g) (0.025 mole) of 2,2,2-trifluoro-
ethanol, 25 mulliliters ~ml) of trichlor2methane, 3.8 g (0.025 mole) of
p-chlorophenyliso~yanate, 3 drops of triethylamine and 1 ~rop o dibutyl
tin dilaurate were combined, stirred at room temF~rature for 15 munutes,
refluxed for t~3 hours, ccoled~a~d evaporated. Yield was 6 1 g of 2,2,2-
trifluoroethyl p-chlorophenyl carbamate. m.p. = 5~-57C. Structure was
confirmed by infrared spectroscopy.
m e N,N-diallyl dichloroacetamude ccmpound of this invention may
be prepared acoording to the followin~ procedure. Three and seven-tenths
grams ~3.7 g) (0.025 mole) of dichloroacetyl chloride were dissolved in -
100 milliliters (ml~ of dichlor~methane and cooled to 5C in an ioe bath.
Four and nine-tenths g (4O9 9) (0.05 m~le) of diallylamine were added
slowlyp and the temperature was maintained at about 10C.
Ihe reaction mixture was stirxed at rocm temperature for four
hours, washed twice with water, dried over magnesium sulfate, filtered
~nd stripped. Yield was 4.0 ~ of diallyl dlchloroacetamide. nD30 - 1~4990
Structure was confirm~d ky infrared and nuclear m~gnetic resonance spec-
troscopy.
Testinq
A stock solution of the pyrroli~one was prepared by d~lutinq
the requisite am~unt of the herbicide in water cr in an acetone-water
solution. Examples of solution compositions and application rates are
su~marized in Table I.
s
`'
, . . . ~ . . .
37~
I~BLE I
Herbicide Stock Solutions
Cc~p~sition ~
DR~IDlD7D~ SDl---7~5ob9~ pplication
Herbicide Name ~m~)* (ml) (ml) ml/f~at** l~ e
methylphenyl-3- 781 100 2.67 1.25
chloro-4-chloro-
methyl-2- 122 20 20 2.73 0.5
pyrrolidone
* The weight is measured in terms of mg of a 2E formulation of the herbi-
cide, ~hat is, 2 lb of active in~redient per gallon of liquid fo~mula-
tion.
** The flats measure 5.95 inches by 9.5 inches. Approximately four (4)
m~/flat is equal to one (1) lb/acre.
In all cases, the herbicide was applied to the surface of the
soil after planting the seeds and prior to emergen~e of the plants, that
is, by pre-emergence surface application. m e herbicide is sprayed on the
soil either in a tank-mix with the antidote or alone after pre-emergence
surface application, pre-plant incorporation or in-furrow appli~ation of
the antidote.
Stock solutions of the above named antidote compounds were pre-
pare~ at the desired concentrations by diluting the requisite amount in
acetone or in an acetone-water solution. Examples oE solution composi-
tions, rates and application methcds are summarized in Table II.
T~BLE II
ntidote Stock Solutions
Composition Water _ Application
ml7~---t lb/acre Method
__
- n. 30 1.00 IF**
- 1.50 5.00 IF
2.67 1.00 PES***
300 20 20 2.67 5.00 PFJS
* Antidote is ~t technical grade.
** IE' = In-~rrow surface application of antidote.
*** PES = Pre-emergent surface application.
~ 1~337q:~
The antidote solutions were applied to the soil either by in-
furrcw surface application, by pre-plant incorporation or by pre-ernerqence
surface application usinq an atomizer or a linear spray table.
For in-furrow application, a one pint (473 cubic centimeters
(cc)) sample of soil containin~ the previously incorporated herbicide was
removed and retained fram each planting flat. After levelin~ and furrow-
ing the soil, seeds of the crop or weed species were planted 1/2 inch deep
(1027 centimeter). Each flat was divided in half by a wooden barrier. A
stock solution of the antidote was atomized directly onto the e~posed
seeds and soil in the open furrow on one side of the barrierO The seeds
in the entire flat were then covered with the previously removed 50il.
m e antidotally untreated sections of flats were cnrapared for observed
differences which would ir~icate lateral movement of the antidote throu~h
the soil.
A few of the antidotes in the followinq tests were combined with
the soil prior to planting the seeds. Such application is called pre-
plant incorporation. Stock solutions of t~le antidote were injected into
the soil in a 5-gallon cement mixer and mixed in proportions necessary to
achieve the desired rates. The soil with lhe antidote was then trans-
ferred to flats, leveled and furrowed into rows 1/2 inch deep. Enough
seeds were planted to obtain good stands in each treatment. ~he seeds
were then c~vered with the antidote treated soil.
Control flats ~ontained crops tre~ted with herbicide only.
All flats were placed on greenhouse benches where temperature was main-
tained between 70 and 9nF (21.1 to 32.2C). The flats were watered bysprinkling as needed to assure good plant growth~
All of the soil used in the tests described herein was loamy
sand soil treated with 50 parts per million ~ppm) each of a ccmmercially
available f~gicide, N-~(trichloromethyl)-thio]-4-cyclohexene 1,2-dicar-
hoximide, and 18-18-18 fertilizer, which contains 18~ by weight equivalent
each of nitrogen, phosphorus pentoxide, and potassium oxide.
~37~
Injury ratings were taken four weeks after application of the
antidote. The effectiveness of the antidote was determined by visual oom-
parison of crop injury which occurr~d in the test flats to that which
occurred in the control flatsO
'rhe treated crops initially screened for diminution of herbici~
dal injury were milo, wheat, cotton, rice, barley, corn and soybeans. The
compounds were also tested on weed species. The weed species tested
included watergrass (Echinochloa crusgalli~, Eoxtail (Setaria viridis),
_ __ ___ _ _
wild oat (Avena fatua) and mustard (Brassica spp.)
Herbicides
l-m-TriEluoromethylphenyl-3-chloro-4-chloromethyl 2-pyrrolidone
N~m-Cyanophenyl-3-chloro-4-chloromethyl-pyrrolidone-2
Applicatlo ethods
IF = In furrcw surface application of antidote Isoil subsequently
treated with herbicide only).
PPI = Pre-plant incorporation of the antidote.
PES = Pre-emergence surface application of herbicide or antidote.
TM ~ Tank-mi~ed solution of herbicide and antidote.
If no antidote was applied, the w~rd 'Inone" appears in the Anti-
dote Rate columnO Ihe results shown on this line are the percent injuries
sustained by each of the crops when treated wi~h the herbicide only at the
rate specified.
All rates shown, for both herbicide and antidote, are in po~nds
per acre.
I ury Ratings
The injury to the crops (Tables III, V, VII, and IX) cr weeds
(Tables IV, Vl, VIII and X) is shown as a percentage of damage done to the
plants as compared to an evaluation of the overall undamaged state of the
plants. '~he damage done to the plants is a function of the n~mber of
plants injured ,~d the extent of in~ury to each plant. This rating is
1 ~37~
made four (4) weeks after applicaticn of ~he herbicide alone or of the
herbicide in combination with the an~idote.
An asterisk (*) in Tables III, V, VII, and IX indicates that the
antidote coTpound is active in reducing herbicidal in~ury to the cropO
~ables IV, VI, VIII and X show that the antidote compounds
tested have no effect on weeds, i.e., herbicidal injury to the weeds is
sustained even in the presence of the antidote compound.
3~
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TABLE rv
_ _
Herbicidal Effectiveness
Antidote: N~Ethyl-N-benzyl-dichloroacetamide
Antidote Antidote Water- Fox- Wild
Herbicide ~ate Rate -Method qrass tail Oat Mustard
l-m-trifluoro- 0.50 none ~ lOO lOO
methylphenyl-3- 0.50 loOO IF lOO lOO
chloromethyl-2- 0.50 5~00 IF lOO lOO
pyrrolidone
0.50 none ~ lOO lOO
0.50 l.OO PES lOO lOO
0.50 2.00 PES lOO lOO
0.50 none - lOO lOO
0050 l.OO IF lOO lOO
0.50 5.00 IF lOO lOO
0.50 none - lOO lOO 90 lOO
0.50 1.00 PES lOO lOO 90 lOO
0.50 5.00 PES lOO lOO 90 lOO
0.50 none - lOO
0.50 5.00 IF lOO
0.50 none - lOO lOO
0.50 l.OO IF lOO lOO
0050 5.00 IF lOO lOO
0.50 none - lOO lOO
0. 50 1 . 00 PES 100 100
O.50 2.00 PES lOO lOO
O.50 5.00 PES lOO lOO
0.50 none - lOO lOO
~. 50 1 . 00 IF 100 100
0.50 5.00 IF lOO lOO
0.50 none - lOO lOO 90 lOO
0.50 l.OO PES lOO lOO 90 lOO
0.50 5.00 PE~ lOO lOO 90 lOO
0.50 none - 90
0.50 5.00 IF 90
0.75 non~ - lOO
O.75 5.00 PES lOO
~,3~
16
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18
TABLE Vl
_.
~lerbicidal Effectiveness
Antidote: 2,2,2-Trlfluoroethyl-N-p-chlorophenylcarbamate
Percent Injury
Antidote Water-
Herbicide Rate Rate Method Mustard qrass Foxtail
l-m-trifluoro, 0.50 none - 80 90 lOn
methylphenyl-3-0.50 l.00 IF 80 90 lO0
chloromethyl-2-0.50 2000 IF 80 90 lO0
pyrrolidone 0.50 5.00 IF 80 90 lO0
O.50 none - 80 90 lO0
O.S~ 1.00 P~S/TM 80 80 lO0
0.50 2.00 PES/IM 80 90 lO0
.50 S0OO PES/TM 80 ~0 lO0
0.75 none - 85 lO0 lO0
0.75 l.00 IF 85 lO0 lO0
0.75 2.00 IF 85 lO0 lO0
0.75 5.00 IF 85 lO0 lO0
0~75 none 85 lO0 lO0
0.75 l.00 PES/qM 85 lO0 lO0
0.75 20 00 PES~RM 85 lO0 lO0
0.75 5.00 PES/'~M~5 lO0 lO0
1.00 none - lO0 lO0 lO0
l.00 l.00 IF lO0 lO0 lO0
l.00 2.00 IF lO0 lO0 lO0
l.00 5.00 IF lO0 lO0 lO0
l.00 none - lO0 lO0 lO0
1.00 1.00 PES/.~ 100 100 100
1.00 2.00 PES/'nMlO0 lO0 lO0
1~00 5~00 PES/r[M100 100 100
2.00 none - lO0 lO0 lO0
2~00 l.00 IF lO0 lO0 lO0
2.00 2.00 IF lO0 lO0 lO0
2.00 5.00 IF lO0 lO0 lO0
2.00 none - lO0 lO0 lO0
2.00 l.00 PES/TM lO0 lO0 lO0
2.00 2.00 PES/TM lO0 lO0 lO0
2.00 5.00 P~S/TM lO0 lO0 lO0
~837~$
19
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22 ~37~
Test Results
Ihe compositions of Fyrrolidone herbicides and antidote com-
pounds were effective for the reduction of herbicidal in~ury to a wide
variety of crops~ Use of the antidote oompounds did nDt result in a
reduction of herbicidal iniury ~o weeds.
Fonnulations
A fonn~llation is the incorporation of a fo~nulant in a form
which is directly usable on crops and weeds. As defined herein, a "fonnu-
lant" is the material which is to ke formulated. The fonnulant rnay beeither an antidote o~mpound alone or an herbicide and antidote composi~
tion. The purpose of th.e fonnulation is to apply the forrnulant to the
locus ~lere it is desired to establish herb.icidal selectivity by a conven-
lent method~ me "locus" may .include soil, seeds, seedlings and vegeta-
tion.
The formulations are commonly dusts, wettable powders, granules,solutions or emulsifiable concentratesO
Dusts are free Elowing powd~r co~positions containing the formu-
lant impregnated on a particulate carrier. The particle si.ze of the car-
riers is usually in the approxlmate ran~e o~ 30 to 50 mic~ons. Examplesof suitable carriers are talc, bentonite, diatomaceous ear~h, and pyro-
phyllite. The oo~position generally contains up to 50% of fonmulant.
Anti-cakinq and anti-static agents may also be added. ~usts may be
applied by spraying ~rom bcom and hand sprayers on airplanes.
,. . , - - ; ~ .
23 ~3~
Wettable pcwders are finely divided compositions oomprising a
particulate carrier impreqnated with the formulant and additionally ~on~
taining one or mor~ surface active a~ents. '~he surface active aqent pro-
motes rapid disper~ic,n of the pcwder in an aqueous medium to form stable,
5 sprayable suspensions. A wide vclriety of surface active aqents can be
used, for example, long chain fatty alcohols and alkali metal salts of
the sulfated fatty alcohols; salts of sulonic acid; esters of long chain
fatty acids, and polyhydric alcohols, in which the alcohol group6 are
free, omegasubstituted polyethylene glycols of relatively long chain
length. A list of surface active agents suitable fcr use Ln agriculture
formulations can be found in ~ade Van Valkenburq~ Pesticide Formulations
~Marcel Dekker, Inc., N.Y., 1973) at pages 79-84.
Grc~nules comprise ~he formulcant impregnated on a particulate
inert carrier having a p2rticle size of about 1 to 2 millimeters (~m) in
diameter. Ihe granules can be maAe by spraying a solution of the formu-
lant in a volatile solvent onto the granular carrierO Exa~ples of suit
able carriers for the preparation of granules ind ude clay, vermiculite
saw~ust, and granular carbon.
Emulsifiable concentrates consist o an oil solution of the
formulant plus an emulsifying agent. Pric,r to use the concentrate is
diluted with water to form a suspended emulsion of oil droplets. The
emulsifiers used are usually a mixture of anionic and nonionic surfac-
tants. Other additives~ such as suspending agents and ~hickeners, may
in d u~ed in the emulsifiable cDncentrate.
~hen the formulant is an antidote and herbicide oonposition,
the proportion of antidote compound to herbicide oompound generally
ran~es from approx~mately 0.00l to 30 parts by weight of the antidote
compound per weight of the herbicide compound.
Formulations generally oontain several additives in addition to
the formulant and carrier or agent. Among these are inert ingredients,
diluent carriers~ organic solvents, water, oil and water, water in oil
emulsions, carriers of dusts and granules, and surface active wetting,
dispersiny a~d emulsifying agents. Fertilizers, e.~., ammonium nitrate
24 ~i3~
urea and superphosphate, may be included. Aids to rcotin~ and growth~
e.g., oompost, manure, humus and sand, may also be included.
Alternatively, the antidote compounds and herbicide and anti-
dote compositions of this invention can be applied to a crop by addition
of the formulant to irrigation water supplied to the field to be treated.
This method of application permits the penetration of the compositions
into the soil as the water is absorbed.
As another alternative, the formulant can be applied to the
50il in the form of a solution in a suitable solvent. 501vents frequent
ly used in these formulations include kerosene, fuel oil, xylene, petrol-
eum fractions with boilin~ ranges above xylene and aromatic petroleum
fractions rich in methylated naphthalenes. Iiquid solutions, like dusts,
may be applied by spraying frcm boom and hand sprayers on airplanes.
