Note: Descriptions are shown in the official language in which they were submitted.
~040~50
Back~round of the Invention
Among the many herbicidal compound~ co~mercially avail-
able, the thiocarbamates alone or admixed with other herbicides,
such as the triazines, have reached a relatively high degree of
commercial success. These herbicides are immediately toxic to a
large number of weed pests at different concentrations varying
with the resistance of the weed pests. Some examples of these
compounds are described and claimed in the U.S. Patents No.
2,913,327, 3,037,853, 3,175,897, 3,185,720, 3,198,786 and
3,582,314. It has been found in practice that the use of these
thiocarbamates as herbicides on crops sometimes causes serious
in~uries to the crop plant. When used in the recommended amounts
in the soil to control many broadleaf weeds and grasses, serious
malformation and stunting of the crop plants result. This abnor-
mal growth in the crop plants results in loss of crop yield.
Previous attempts to overcome this problem involves the treat-
ment of the crop seed with certain antagonistic agents prior to
planting, see U.S. Patents No. 3,131,509 and 3,564,768. These
antagonistic agents have not been notably successful. The afore-
mentioned patent specifically exemplifies the treatment of seeds
employing compounds of a different chemical class not suggestive
of the present invention.
. ''
. ~
~ . 104Q450
Description of the Invention
It has been discovered that plants can be protected '~
against injury by various herbicides of the thiocarbamate-type
or substituted acetanilide-type, alone or mixed with other com-
pounds and/or the tolerance of the plants can be substantially
increased to the active compounds of the above-noted U.S.
Patents by adding to the soil an antidote compound corresponding
to the following formula:
wherein Rl is selected from the group consisting of di-p-chloro-
phenylmethyl, phthalimidomethyl, pentachlorophenyl, alkenyl,
chloroalkenyl, aminoalkylj hydroxyethyl, carboxymethyl, N-alkyl-
carbamoylmethyl, haloalkyl, mono-chlorobenzamidoethyl, dichloro-
benzamidoethyl, mono-bromobenzamidoethyl, ~-S-ethylthiocarboxyl-
aminoethyl and dichloroacetamidoethyl; and R2 is selected from
the group consisting of p-chlorophenyl, alkyl, haloalkyl, ~-
hydroxytrichloroethyl, alkenyl, chloroalkenyl, aminoalkyl, cyano-
alkyl, cyanochloroalkyl, mono-chlorobenzylamidoethyl, dichloro-
benzamidoethyl, mono-bromobenzamidoethyl, ~-S-ethylthiocarboxyl-
aminoethyl and dichloroacetamidoethyl.
In the above description, the following embodiments
are intended for the various substituent groups: For Rl,
alkenyl perferably includes those members containing at least one
olefinic double bond and from 3 to 6 carbon atoms, inclusive, in
both branched and straight chain configurations; chloroalkenyl
includes mono-, di-, tri- and tetra-chloro substitution in alkenyl
moieties having 3 to 6 carbon atoms, inclusive; the term amino-
. .. .
'~. alkyl includes those members having at least one amino group
.~.
,.,
- 3
1040450
(NH2-) and an alkyl moiety having from 1 to 6 carbon atoms,
inclusive. For R2~ alkyl preferably includes those members
having from 1 to 8 carbon atoms, inclusive, in both branched
and straight chain configurations; alkenyl preferably includes
those members containing at least one olefinic double bond and
from 3 to 6 carbon atoms, inclusive, in both branched and
straight chain configurations; chloroalkenyl includes mono-,
di-, tri- and tetra-chloro substitution in alkenyl moieties
having 3 to 6 carbon atoms, inclusive; aminoalkyl includes those
members having at least one amino group (NH2-) and an alkyl
moiety having from 1 to 6 carbon atoms, inclusive; cyanoalkyl
includes those members having at least one cyano group (-C~)
and an alkyl moiety having from 1 to 4 carbon atoms; cyano-
chloroalkyl includes those members having at least one cyano
group, from 1 to 4 chlorine atoms, inclusive, and an alkyl
moiety having from 2 to 6 carbon atoms, inclusive. The term
haloalkyl preferably includes those alkyl members substituted
with at least one halogen, selected from chlorine and bromine
and having from 1 to 4 carbon atoms.
As an alternative mode o action, the compounds of
this invention may interfere with the normal herbicidal action
of the thiocarbamate-type and other herbicides to render them
selective in their action. Whichever mode of action is present,
the corresponding beneficial and desirable effect is the con-
tinued herbicidal effect of the thiocarbamate or other herbicide
; with the accomp~nying decreased herbicidal effect on desired
crop species. This advantage and utility will become more
apparent hereinafter.
.
104Q450
; Therefore, the terms herbicide, antidote or anti~otal
amount, is meant to describe that effect which tends to counter-
act the nonmal injurious herbicidal response that the herbicide
might othe~ise produce. Whether it is to be termed a remedy,
interferant, protectant, safening agent, or the like, will depend
upon the exact mode of action. The mode of action is varied, but
the effect, which is desirable, is the result of the method of
treating the soil in which a crop is planted. Hitherto, there
have been no systems which have been satisfactory for this purpose.
The compounds of this invention represented by the
above formula can be prepared by several different procedures
depending upon the starting materials.
General Procedure for Preparation of Allyl and BenzYl Sulfides
The active halide (allyl or benzyl type) is dissolved
in isopropyl alcohol or other suitable solvent, and sodium sul-
fide nona-hydrate which had been coarsely ground was added. The
addition is at reduced temperature, approximately 15C. At the
end of the reaction, the precipitated sodium chloride is removed
by filtration and the solvent removed in vacuo. The residue is
taken up in benzene and ether and washed with three portions of
water. The solution is dried and the solvent distilled in vacuo
.~
General Procedure for Preparation of Mixed Sulfides
An organo mercaptan is dissolved in a suitabLe solvent,
such as dioxane, isopropyl alcohol or the lil~e. Sodium hydroxide
~, solution is added and the reaction mixture heated. An active
organo halide is added and the mixture refluxed. Wor~-up is by
normal procedures of extraction, solvent removal, distillation or
crystallization,
.
, _5_
104~450
The compounds and the present invention and their pre-
paration are more particularly illustrated by the following
examples. Following the examples of preparation is a table of
compounds which may be prepared according to the procedures
described herein. Compound num~ers have been assigned to them
and are used for identification through the balance of the
specification.
EXAMPLE'I
Preparation of bis-(3,3-dichloroallyl)-sulfide
1,1,3-trichloropropene-1 (1100 g., 7.5 M) was dissolved
in one liter of isopropanol and sodium sulfide nona-hydrate
(900 g., 3.75 M) which had been coarsely powdered, was added
at one time at 15C. The mixture was stirred at 25-30C. for
3 hours and at 50C. for 2 hours. It was allowed to stand over-
night at room temperature. The precipitated sodium chloride was
filtered off and the solvent removed in vacuo. The residual oil
was taken up in a mixture of one liter of benzene and one liter
of ether and washed with three 400 ml. portions of water. The
solution was dried over magnesium sulfate and the solvent re-
moved in vacuo. The residual solvent was removed at about 0.5 mm.
There was obtained a red brown liquid, yield: 853 g. (90%).
Structure was confirmed by NMR spectroscopy. The product
distilled at b.p. 75-77/35mm.
"
~0404S0
EXAMPLE II
Pre~aration of bis~ m-chlorobenzamidoethyl)sulfide.
To a solution of bis-( ~ -aminoethyl)sulfide (2.5 8 ,
0.021M) and sodium hydroxide (1.6 g., 0.04 M) in 20 ml. of water
and 40 ml. of ether was added a solution of m-chlorobenzoyl
chloride (7.0 g., 0.04 M) in 15 ml. of ether at 10-20C. A
precipitate appeared. The mixture was stirred 45 minutes at
; room temperature and the solid filtered, washed with water and
dried. The product was a white solid. m.p. 150-152C. Its
structure was confirmed by IR spectroscopy. Yield: 7.0 g. (8870).
, . .
,;, .
,
' ' '
-7
10404S0
~ TABLE I
Rl-S-R2
m.p. C.
COMPOUND Rl R2 o r NDO
1 (Cl-phenyl)2CH p-Cl-phenyl 1.6460
2 ~ \~ CH CH(CH3)2 57-62
: O
o
; 3 CH2C-NHCH2cH~cH3)2 p-Cl-phenyl 107-112
O
Il
4 ~ " " N-CH2 CH2CH3 64-72
O
1OI
~ / N CH2 CH2CH2CH3 1.5561
O
Cl ~ CH2CH2C1 133-134
C
OIH
7 p-Cl-phenyl CHCC13 73-76
8 CC12=CHCH2 CC12-CHCH2 75-77/35mm.
9 phenyl CC12CH2C - N 1.6073
CC12=CClCH2 CH2CH3 1.5325
11 CH3CCl=CHCH2 CH3CCl=CHCH2 1.5387
~`, O
12 CH2C-OH CH2C N 1.5217
~:
--8--
- ~ ;
TABLE I (continued)
104~450
m.p. c.
COMPOUND Rl R2 or N30
13 CHCl-CHCH2 CHCl=CHCH2 1.5270
14 CH2CHCH2 CH2=CHCH2 1.4850
HOCH2CH2 CH3CH2 1.4816
16 CC12=CClCH2 CC12=CClCH2 1.5810
17 phenyl CH2CH=CC12 1.5905
18 ClCH2CH2CH2 CH2CH2CH2C1 1.4528
19 HOCH2CH2 n C8H17 1.4710
; 20 . H2N-CH2CH2 CH2CH2NH2 b p 64^6~C.
O
21 C2H5SCNHcH2cH2 CH2CH2NHCSC2H5 130-132
22 ~ C~-NHCH2CH2 CH2CH2NHC ~ 148-lSl
23 ~ CNHCH2CH2 CH2CH2NHC ~ 150-152
' C
24 ~ C-NHCH2CH2 CH2CH2NHC ~ 170-172
Br Br
Cl-CH=CCl-CH2 CH2CCl=CHCl red/bro~n
O O
26 C12CHC~HCH2CH2 CH2CH2NHCCHC12 111-115
The compounds of this invention were employed in effec-
~; tive herbicidal antidote compositions comprising thiocarbamates
or substituted acetanilides in combination with antidote compo~nds
described hereinabove. They were tested in the following manne~.
_g_
104V4S0
Corn Seed Treatment Test
Small flats were filled with Felton loamy sand soil.
Soil incorporated herbicides were applied at this time. The soil
from each flat was placed into a five-gallon cement mixer where
the soil was mixed as the herbicides were applied using a pre-
determined amount of a stock solution containing 936 mg. of
75.5% active ingredient to 100 ml. of water. One ml. of stock
solution was applied to the soil in a volumetric pipet for each
pound of herb cide desired. One ml. of stock solution contained
7 mg. of herbicide which equals one pound per acre when applied
to the soil in the flats. After the herbicide incorporation, the
soil was placed back into the flats.
Flats of herbicide-treated and untreated soil were
then ready to be planted. A pint sample of soil was removed
from each flat and placed next to each flat for later use in
covering up the seeds. The soil was leveled and rows one-half
inch deep were made for planting seeds. Alternating rows of
treated and untreated crop seeds were sown. In each test, six
DeKalb XL 374 field corn seeds were planted in each row. Rows
were approximatley 1-1/2`inches apart in the flat. Seeds were
treated by placing 50 mg. of the antidote compound with 10 grams
of corn seed in a suitable container and shaking them until the
seeds were uniformly covered with the compound. Antidote com-
pounds were also applied as liquid slurries and powders or dusts.
In some cases, acetone was used to dissolve powdered or solid
compounds so they could be more effectively applied to the seeds.
- -- 10 --
~040450
After the flats were seeded, they were covered with the
one pint of soil which had been removed 3ust prior to p~anting.
Flats were placed on gxeenhouse benches where temperatures ranged
from 70-90F. Flats were watered by sprinkling as needed to
assure good plant growth. Per cent control ratings were taken
two to three weeks after the treatments were applied.
:
; In each test, the herbicide was applied alone, in com-
bination with the seed protectant, and the seed protectant was
applied alone to check for phytotoxicity. The untreated adiacent
row was employed to observe any beneficial laterial movement of
the antidote compound through the soil. The degree of the effect
was noted by comparison with the control. The results of these
tests are tabulated in Table II.
~ TABLE II
- Per Cent IniurY to Corn from EPTC*
Seed Treatment Test
Per Cent IniurY weeks
Treated Untreated
COMPOUND EPTCSeed Seed
fl _NU~IBER lb/A(0.5% w/w) (2 wks) Adjacent Row (3 wks)
1 6 50 50
2 6 40 65
3 6 50 80
4 6 65 70
; 5 6 80 70
EPTC
Untreated
Seed -_ go __ -
* = S-ethyl dipropylthiocarbamate
.
-11-
:,
1040450
Procedure: Multicrop Antidote Screen
Flats were filled with Felton loamy sand soil. A
variety of grass and broadleaf crops were used in these tests.
EPTA ~ (EPTC) was incorporated at 1/2, 3 or 5 lb/A, while a
constant rate of 5 lb/A of the additive was used. LASS ~
(EPTC) or ORD ~ (S-ethyl hexahydro-1-H-azepine-l-carbothioate)
and the candidate herbicide antidote were applied separately by
; pipetting measured amounts of the appropriate stock solutions
into the soil during incorporation in a 5 gallon rotary cement
mixer. Stock solutions were prepared as follows:
A. 1 2 lb/A: 670 mg. of EPTC 6E (75.5% a.i.) is
diluted with 500 ml. of deionized water so that
2 ml. equals 1/2 lb/A flat.
B. 5 lb/A: 6700 mg. of EPTC 6E (75.5% a.i.) is
diluted with 500 ml. of deionized water so that
2 ml. equals 5 lb/A flat.
C. 2 lb/A: 427 mg. LASSO 4E is diluted with 100 ml.
of deionized water so that 1 ml. equals 2.05 mg.
(a.i.) and 4 ml. equals 8.2 mg. equivalent to
2 lb/A flat.
D. 6 lb/A: 4312 mg. of ORDRAM 6E (71.3~ a.i.)
was diluted with 500 ml. of deionized water so
that 4 ml. of the stock solution equaled 6 lb/A
when applied to a flat.
Antidote stock solutions are prepared by diluting
102 mg. of technical material with 10 ml. of acetone 1% Tween 20
(polyoxyethylene sorbitan monolaurate) so that 2 ml. equals
5 lb/A flat.
After the soil is treated with both herbicide and
additive, the soil is transferred from the mixer back into the
flat where it is then prepared for seeding. The initial step in
preparation is to remove a one pint sample of soil from each
,t
- 12 -
1()4~)450
flat to be retained and used to cover the seeds after planting.
The soil is then leveled and rows one-quarter inch deep are made
in each flat. Flats treated with the herbicide and additive are
seeded with corn (Zea maize), sugarbeets (Beta vulgare), sun-
flower (Helianthus annus), cotton (Goss~ypium hirsu'tum), soybeans
; (Glycine max)' and oilseed rape (Brassica napus). Flats treated
with 1/2 lb/A of EPTAM are seeded with red oats (Avena Byxantina),
milo (Sorghum vulgare), wheat (Triticum aestivum), giant foxtail
(Seteria feberii), rice (Oryza sativa) and barley (Hordeum
vulgare). Flats treated with 2 lb/A of LASSO are seeded with
corn (Zea maize), wheat (Triticum aestivum), rice ~-Oryza sativa),
milo (Sorghum vulgare), and barley (Hordeum vul~are). Seeds are
' then covered with the pint soil sample removed prior to seeding.
The flats are then placed on greenhouse benches
where temperatures are maintained between 70-90F. The soil is
watered by sprinkling to assure good plant growth.
, Injury ratings are taken at 2, 3 or 4 weeks after the
treatments are applied. Soil treated with the herbicides alone
at V 2, 2, 3, 5 or 6 lb/A is included to provide a basis for
20 determining the amount of injury reduction provided by the herbi-
cide antidotes. The per-cent protection is determined by a
comparison with flats not treated with the candidate antidote,
- but with the herbicide alone. Results are given in Table III.
;
'.~
- 13 -
1040450
TABLE III
MULTICROP SCREEN RESULTS
PER CENT PROTECTION
Rate of % Pro-
COMPOUND Rate of Antidote tecti~
NUMBER Herbicide lb/A lb/A Crop (4 ~ks~
6 EPTCa 3.0 5.0 corn lOQ
EPTC 3.0 5.0 soybeans 40
7 EPTC 3.0 5.0 corn 75
8 EPTC O.5 5.0 sorghum 10
EPTC 0.5 5.0 rice 30
EPTC 3.0 5.0 corn 10~
ORDRAMb 6.0 5.O rice 72
LASSOC 2 0 S O wheat 38
LASSO 2 0 5 0 sorghum 100
9 EPTC 0.5 5.0 sorghum 50
: EPTC 0.5 5.0 rice 44
EPTC 3.0 5.0 mustard 100
11 EPTC 0~5 5.0 sorghum 50
EPTC 0.5 5.0 rice 38
EPTC 3.0 5.0 corn 67
12 EPTC 3.0 5.0 corn 10~
13 EPTC 5.0 5.0 sunflower67 (3)
14 EPTC 0.5 5.0 rice 100 (3)
ORDRAM 6.0 5.0 rice 30
EPTC 0.5 5.0 rice 100 (3)
16 EPTC 0.5 1.0 rice 11
17 EPTC 0.5 5.0 80 rghum 67
EPTC 3.0 5.0 corn 83
18 EPTC 0.5 5.0 barley 45
19 EPTC 5.0 5.0 sunflower 67
EPTC 5.0 5.0 rape 87
21 EPTC 0.5 5.0 rice 86
22 EPTC O 5 5 0 rice 100
EPTC 5 0 5 0 sunflower 75
-14-
TA~LE III (continued) 1~409~50
Rate of % Pro-
CO~OUND Rate of Antidote tection
NU~E~ Herbicide lb/h lb/A CroP (4 wks)
23 EPTC 0.5 5.0 rice lOO
EPTC 5.0 5.0 sunflower 75
24 EPTC 0.5 5.0 rice 62
EPTC 5.0 5.0 corn 15
26 EPTC 5.0 5.0 corn 45
a = S-ethyl dipropylthiocarbamate
b = S-ethyl hexahydro-lH-azepine-l-carbothioate
c = 2-chloro-2',6'-diethyl-N-(methoxymethyl)acetamide
The antidote compounds and compositions of the present
invention can be used in any convenient form. Thus, the antidote
compounds can be formulated into emulsifiable liquids, emulsifi-
able concentrates, liquid, wettable powder, powders, granular
or any other convenient fo m, In its preferred form, a non-
phytotoxic quantity of an herbicidal antidote compound is admi~ed
with a selected herbicide and incorporated into the soil prior
to or after planting the seed. It is to be understood, however,
that the herbicides can be incorporated into the soil and there-
after the antidote compound can be incorporated into the soil.
Moreover, the crop seed itself can be treated with a non-phytotoxic
quantity of the compound and planted into the soil which has been
treated with herbicides, or untreated with the herbicide and sub-
sequently treated with the herbicide. The addition of the anti-
dote compound does not affect the herbicidal activity of the
herbicides.
-The amount of antidote compound present can range
between about 0.01 to about 15 parts by weight of antidote com-
pound described herein per each part by weight of herbicide.
-15-
,
1040450
The exact amount of antidote compound will usually be deter~ined
on economic ratios for the most effective amount usable. It Ls
understood that a non-phytotoxic quantity of antidote compound
will be employed in the herbicidal compositions described herein.
The herbicides indicated in the tables and elsewhere
are used at rates which produce effective control of undesirable
vegetation. The rates are within the recommended amounts set
; forth by the supplier. Therefore, the weed control in each ia-
stance is commercially acceptable within the desired or reco~-
mended amount.
It is clear that the classes of herbicidal agents d~s-
cribed and illustrated herein are characterized as effective
herbicides exhibiting such activity. The degree of this herbL-
cidal activity varies among specific compounds and among combi-
nations of specific compounds within the classes. Similarly,
the degree of activity to some extent varies among the species
of plants to which a specific herbicidal compound or combinati~n
may be applied. Thus, selection of a specific herbicidal com-
pound or combination to control undesirable plant species readily
may be made. Within the present invention are prevention of
injury to a desired crop species in the presence of a specifLc
compound or combination may be achieved. The beneficial plznt
species which can be protected by this method is not intended to
be limited by the specific crops employed in the examples.
; 25 The herbicidal compounds employed in the utility o~
this invention are active herbicides of a general type. That is,
` the members of the classes are herbicidally effective against a
.
~'
-16-
. .
104~450
wide range of plant species with no discrimination between desir-
able and undesirable species. The method of controlling vege-
tation comprises applying an herbicidally effective amount of
the hereindescribed herbicidal compounds to the area or plant
locus where control is desired. The compositions as set forth
in this invention include those wherein the preferred active
herbicidal compound is selected from EPTC, S-ethyl diisobutyl
thiocarbamate, S-propyl dipropyl thiocarbamate, S-2,3,3-tri-
chloroallyl-diisopropyl thiocarbamate, S-ethyl cyclohexyl ethyl
thiocarbamate, 2-chloro-2',6'-diethyl-N-(methoxymethyl)~cetanilide,
S-ethyl hexahydro-lH-azepine-l-carbothioate, 2-chloro-N-isopropyl-
acetanilide, N,N-diallyl-2-chloroacetamide, S-4-chlorobenzyl
diethyl thiocarbamate, 2-chloro-4-ethylamino-6-isopropyl2mino-
s-triazine, 2-chloro-4,6-bis(ethylamino)-s-triazine, 2(4-chloro-
6-ethylamine-s-triazine-2-yl-amino)-2-methylpropionitrile,
2-chloro-4-cyclopropylamino-6-isopropylamino-s-triazine, 2,4-di-
chlorophenoxyacetic acid, its esters and salts, and 3-(3,4-di-
chlorophenyl)-l,l-dimethylurea and combinations thereof.
An herbicide as used herein means a compound which con-
trols or modifies the growth of vegetation or plants. Such con-
trolling or modifying effects include all deviations from natural
development; for example, killing, retardation, defoliation,
desiccation, regulation, stunting, tillering, stimulation, dwarf-
ing and the like. By "plants", it is meant germinant seeds, emer-
ging seedlings, and established vegetation, including the roots
; and above-ground portions.
-17-
