Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
VCC-4579
~ D-1523
TETRAHYDROBENZOTHIAZOLYLI~IDAZOLIDINONES
Specification
This invention relates to new compositions of ~atter. More
specifically, this invention relates to new chemical compounds of the
formula
n ~ OH
o (I)
~herein X is selected from the group consisting of alkyl, alkoxy, alkylthio,
halogen, dialkylamino and cyano; n is an integer from O to 4; and R is se-
lected from the group consisting of alkyl, alkenyl, haloalkyl and alkynyl.
The compounds of the present invention are unexpectedly useful
- 15 as herbicides and are particularly effective in the post-emergence con-
trol of weeds.
In a preferred embodiment of this invention X is selected from
the group consisting of lower alkyl, lower alkoxy, lower alkylthio, chlorine,
bromine, di(lower alkyl)amino and cyano; and R is selected from the group
~O consisting of lower alkyl, lower alkenyl, lower chloroalkyl and propargyl.
The compounds of the present invention can be readily prepared
by heating a compound of the formula
~ ~ N ~ OCH3
Xn ~ C - N - C - N - CH2 - CH
2; S H O R OCH3 (II)
3~
wherein X, n and R are as heretofore described, in a dilute, aqueous,
acidic reaction medium for a period of about 10 to about 90 minutes.
Temperatures of from about 60C to the reflux temperature of the
reaction mixture can be utilized. The reaction medium can comprise a
dilute aqueous inorganic acid such as hydrochloric acid at a concentra-
tion of from about 0.5 to about 5 percent. Acidic water-ethanol mix-
tures can also be used. Upon completion of the reactionj the desired
product can be recovered as a precipitate or residue upon cooling or
evaporation of the reaction mixture. This product can be used as such
or can be further purified by conventional means such as recrystalliza-
tion and the like.
The compounds of Formula II can be prepared by reacting a
carbamate of the formula
N ~
n ~ C - N - C - O - Z (III)
wherein Z is methyl or ethyl, and X and n are as heretofore described,
with an acetal of the formula
/ OCH3
H - N - CH2 - C~
R OCH3 (IV)
wherein R is as heretofore described. This reaction can be effected by
dissolving the compound of Formula III in an equimolar or slight molar
excess of the acetal of Formula IV and heating the resulting mixture at
a temperature of from about 90C to about 130 C for a period of from 12
to 4~ hours in a reaction vessel blanketed with inert gas. The reaction
product can then be recovered upon distillation to remove unreacted
starting material and can be used as such or can be further purified if
-- 2 --
~:~Z~'7;~
desired by standard techniques.
The compounds Of Formula III are known in the literature but
when not readily available can be prepared from a compound of the formula
Zn ~ C - ~d~ (V)
wherein Z and n are as heretofore described, by reaction with methyl or
ethyl chloroformate. This reaction can be effected by slowly adding
the chloroformate to a solution of the compound Of Formula III in an:
organic solvent in the presence of an acid acceptor. The acid acceptor
itself may serve as the solvent such as for example pyridine. After the
addition is completed, stirring of the reaction mixture can be continued
to ensure completion of the reaction. After such time the desired
product can be recovered and can be purified by conventional techniques
such washing to remove acid acceptor hydrochloride, recrystallization
and the like.
The compounds Of Formula V when not readily available can be
prepared by the techniques referred to in U. S. Patent 3,682,945.
The compounds of Formula II can also be prepared by reacting
a molar amount of an isocyanate dimer of the formula
[ Zn~ /C - 5 - C - ~ ~
2 (VI)
wherein X and n are as heretofore described, with about two molar amounts
of a dimethyl acetal of the formula
OCH3
H - ~ - CH2 - CH
R OCH3 (VII)
~67~
wherein R2 is as heretofore described. This reaction can be effected by
heating a mixture of the isocyanate dimer and the acetal in an inert
organic reaction medium such as toluene at the reflux temperature of
the reaction mixture. Heating at reflux can be continued for a period
of from about 2 to about 30 minutes to ensure completion of the reaction.
After this time the desired product can be recovered upon evaporation
of the reaction medium and can be used as such or can be further puri-
fied by standard techniques in the art.
The isocyanate dimer of Formula VI can be prepared by reacting
the tetrahydrobenzothiazole of Formula V with phosgene. This reaction
can be effected by adding a slurry or solution of the benzothiazole, in
a suitable organic solvent such as ethyl acetate, to a saturated solu-
tion of phosgene in an organic solvent such as ethyl acetate. The re-
sulting mixture can be stirred at ambient temperatures for a period of
from about 4 to about 24 hours. The reaction mixture can then be purged
with nitrogen gas to remove unreacted phosgene. The desired product can
then be recovered by filtration, if formed as a precipitate, or upon
evaporation of the organic solvent used if soluble therein. This product
can be used as such or can be further purified as desired.
Fxemplary tetrahydrobenzothiazole compounds of Formula ~ suitable
for preparing the compounds of the present invention are:
2-amino-4,5,6,7-tetrahydrobenzothiazole
2-amino-4-chloro-4,5,6,7-tetrahydrobenzothiazole
2-amino-S-methyl-4,5,6,7-tetrahydrobenzothiazole
2-a~ino-7-ethyl-4,5,6,7-tetrahydrobenzothiazole
2-amino-5-hexyl-4,5,6,7-tetrahydrobenzothiazole
2-amino-5-methoxy-4,5,6,7-tetrahydrobenzothiazole
2-amino-5-cyano-4,5,6,7-tetrahydrobenzothiazole
2-amino-5-methylthio-4,5,6,7-tetrahydrobenzothiazole
j
~L~2~7~
2-amino-5,5-diethyl-4,5,6,7-tetrahydrobenzothiazole
2-amino-5-methyl-7-propoxy-4,5,6,7-tetrahydrobenzothiazole
2-amino-5-propylthio-4,5,6,7-tetrahydrobenzothiazole
Exemplary suitable acetals of Formula IV for preparing the
compounds of this invention are the dimethyl acetal of 2-methylamino-
acetaldehyde, the dimethyl acetal of 2-ethylaminoacetaldehyde, the
dimethyl acetal of 2-propylaminoacetaldehyde, the dimethyl acetal of
2-butylaminoacetaldehyde, the dimethyl acetal of 2-pentylaminoacetal-
dehyde and the dimethyl acetal of 2-hexylaminoacetaldehyde.
The manner in which the compounds of the presen~ invention
can be prepared is more specifically illustrated in the following
examples.
Example 1
Preparation of 2-Amino-5,5,7,7-tetramethyl-4,5,6,7-
tetrahydrobenzothiazole
3,3,5,5-Tetramethylcyclohexanone (9.9 grams), cyanamid
(2.1 grams), sulfur (1.6 grams) and ethanol (8 ml) were charged into a
glass reaction vessel equipped with a mechanical stirrer and addition
funnel. Diethylamine (5 ml) was then added dropwise to the reaction
mixture with cooling to maintain the reaction mixture below about 45 C.
After the addition was completed, the reaction mixture was heated at
40 to 45C for a period of 2 hours. After this time the reaction mix-
; ture was poured into water (100 ml) and was acidified with hydrochloric
acid to a pH of 4. The mixture was then washed with ether and the
aqueous phase withdrawn and adjusted to a pH of 9 with aqueous sodiumhydroxide. The resulting mixture was extracted with ether. The ether
extract was l:hen dried over anhydrous magnesium sulfate and evaporated
to yield the desired product 2-amino-5,5,7,7-tetramethyl-4,5,6,7-tetra-
hydrobenzothiaæole as a solid melting at 120 to 122.
-- 5 --
Example 2
Preparation of Ethyl N-(5,5,7,7-Tetramethyl-4,5,6,7-
tetrahydrobenzothiazol--2-yl)carbamate
-
2-Amino-5,5,7,7-tetramethyl-4,5,6,7-tetrahydrobenzothiazole
(16 grams; 0.075 mol) dissolved in pyridine (100 ml) was charged into
a glass reaction vessel equipped with a mechanical stirrer and addition
funnel. Ethyl chloroformate (11 grams; 0.1 mol) was then added dropwise
with stirring and cooling of the reaction mixture. After -the addition
was completed the reaction mixture was allowed to warm to room tempera-
ture and stirring was continued for a period of about 1 hour. Afterthis time the reaction mixture was poured into ice water resulting in a
white precipitate. The precipitate was recovered by filtration, was
dried and recrystallized from methanol to yield the desired product
ethyl N-(5,5,7,7-tetramethyl-4,5,6,7-tetrahydrobenzothiazol-2-yl) carba-
mate having a melt point of 124 to 125C.
Example 3
Preparation of the Dimethyl Acetal of 2- ~1-Methyl-3-(5,5,7,7-
tetramethyl-4 7 5,6,7-tetrahydrobenzothiazol-2-yl)ureido7acetaldehyde
Ethyl N-(5,5,7,7-tetramethyl-4,5,6,7-tetrahydrobenzothiazol-
2-yl)carbamate (2 grams) and the dimethyl acetal of 2-methyl-aminoacetal-
dehyde (20 ml) were charged into a glass reaction flask equipped with
a magnetic stirrer, reflux condenser and gas addition tube. The re-
action misture was blanketed with nitrogen gas and was heated at 120C
for a period of about 50 hours. After this time the reaction mixture
was distilled under reduced pressure to remove excess unreacted starting
material leaving a brown oily residue. This residue was purified by
elution chromotography using ethyl acetate as the èluant. The chroma-
tographed solution was then stripped of solvent to yield the desired
product dimethyl acetal of 2- ~-me-thyl-3-(5,5,7,7-tetramethyl-4,5,6,7-
1~2fi7;~
tetrahydrobenzothiazol-2-yl)ureid ~acetaldehyde as a colorless solid
having a melting point of 108C.
Example 4
Preparation of 1-(5,5,7,7-Tetramethyl-4,5,6,7-tetra-
hydrobenzothiazol-2-yl)-3--methyl-5-hydroxy-1,3-imi-
dazolidin-2-one
The dimethyl acetal of 2- r-methyl-3-(5,5,7,7-tetramethyl-
4,5,6,7-tetrahydrobenzothiazol-2-yl)ureid~acetaldehyde (2.5 grams)
was dissolved in dilute hydrochloric acid (25 ml; 3.7% conc.). The
solution was heated at a temperature of 85C for a period of about
10 minutes resulting in the formation of a precipitate. Additional
hydrochloric acid (15 ml) was added and stirring was continued for
about 90 minutes. After this time the precipitate was recovered by
filtration, was washed with water and dried to yield the desired
product 1-(5,5,7,7-tetramethyl-4,5,6,7-tetrahydrobenzothiazol-2-yl)-
3-methyl-5-hydroxy-1,3-imidazolidin-2-one having a melt point of
135 to 138C.
Example 5
Preparation of 5,5,7-Trimethyl-4,5,6,7-tetrahydro-
benzothiazol-2-yl Isocyanate Dimer
A ~aturated solution of phosgene in ethyl acetate (200 ml)
and 2-amino-5,5,7-trimethyl-4,5,6,7-tetrahydrobenzothiazole (6.0 grams)
were charged into a glass reaction vessel equipped with a mechanical
stirrer and reflux condenser. The reaction mixture was heated at
reflux for a period of about 5 hours. After this time the reaction
was stripped of solvent and unreacted starting materials to yield the
desired product 5,5,7-trimethyl-4,5,6,7-tetrahydrobenzothiazol-2-yl~
isocyanate dimer as a brown crystalline solid.
i7~
Example 6
Preparation of the Dimethyl Acetal of 2- r -Methyl-3-
(5,5,7-trimethyl-4,5,6,7-tetrahydrobenzothiazol-2-yl)-
ureid~lacetaldehyde
5,5,7-Trimethyl-4,5,6,7-tetrahydrobenzothiazol-2-yl isocya-
nate dimer (7.5 grams), the dimethyl acetal of 2-methyl-aminoacetalde-
hyde (5 grams) and toluene (15 ml) ~ere charged into a glass reactionvessel equipped with a mechanical stirrer and reflux condenser. The
reaction mixture was then heatedj with stirring for a period of about
1 hour. After this time the mixture was cooled and filtered. The
filtrate was washed with water, dried and evaporated, leaving the
desired product dimethyl acetal of 2- ~ -methyl-3-(5,5,7-trimethyl-
4,5,6,7-tetrahydrobenzothiazol-2-yl)ureid ~ acetaldehyde as a brown oil.
. .
Example 7
Preparation of 1-(5,5,7-Trimethyl-4,5,6,7-tetrahydrobenzo-
thiazol-2-yl)-3-methyl-5-hydroxy-1,3-imidazolidin-2-one
The dimethyl acetal of 2- r -methyl-3-(5,5,7-trimethyl-
4,5,6,7-tetrahydrobenzothiazol-2-yl)ureid~ acetaldehyde (8.5 grams),
water (25 ml), ethanol (25 ml) and concentrated hydrochloric acid
~8 5 ml) were charged into a glass reaction vessel equipped with a
mechanical stirrer, ther meter and reflux condenser. The reaction
mixture was then heated at reflux for a period of about 10 minutes.
After this time the reaction mixture was stripped of solvents to yield
the desired product 1-(5,5,7-trimethyl-4,5,6,7-tetrahydrobenzothiazol-
2-yl)-3-methyl-5-hydroxy-1,3-imidazolidin-2-one as a brown solid.
Example 8
Preparation of Ethyl N-(5,7-Dimethoxy-4,5,6,7-tetrahydro-
benzothiazol-2-yl)carbamate
2-Amino-5,7-dimethoxy-4,5,6,7-tetrahydrobenzothiazole (0.10 mol)
7~4
dissolved in pyridine (125 ml) is charged into a glass reaction vessel
equipped with a mechanical stirrer, thermometer and addition funnel.
Ethyl chloroformate(0.12 mol) is then added dropwise to the reaction
mixture with stirring and cooling After the addition is completed
the reaction mixture is allowed to warm to room temperature and stir-
5 ring is continued for a period of about 1 hour. After this time the re-
action mixture is poured into ice water to form a precipitate. The
precipitate is recovered by filtration, is dried and recrystallized to
yield the desired product ethyl N-(5,7-dimethoxy-4,5,6,7-tetrahydro-
benzothiazol-2-yl)carbamate.
Example 9
Preparation of the Dimethyl Acetal of 2- r Ethyl-3-(5,7-
dimethoxy-4,5,6,7-tetrahydrobenzothiazol-2-yl~ureid ~-
acetaldehyde
Ethyl N-(5,7-dimethoxy-4,5,6,7-tetrahydrobenzothiaæol-2-yl)-
carbamate (0.08 mol) and the dimethyl acetal of 2-ethylaminoacetalde-
15 hyde (30 ml) are charged into a glass reaction vessel equipped with astirrer, reflux condenser and gas addition tube. The reaction mixture
is blanketed with nitrogen gas and is heated at 125 C for a period of
about 8 hours. After this time the reaction mixture is distilled to
remove excess starting material. The residue is purified by elution
20 chromatography using ethyl acetate as the eluant. The chromatographed
solution is then s~ripped of solvent to yield the desired product di-
methyl acetal of 2-r-ethyl-3-(5,7-dimethoxy-4,5,6,7-tetrahydrobenzo-
thiazol-2-yl)ureid ~acetaldehyde.
_ g _
: , . , : .:
E~ample 10
Preparation of 1-(5,7-Dimethoxy-4,5,6,7-tet~ahydrobenzo-
thiazol-2-yl)-3-ethyl-5-hydroxy-1 3-imidazolidin-2-one
The dimethyl acetal of 2-11-ethyl-3-(5,7-dimethoxy~4,5,6,7-
tetrahydrobenzothiazol-2-yl)ureid ~acetaldehyde (0.05 m~)and dilute
hydrochloric acid (25 ml; 3% conc.) are charged into a glass reaction
vessel equipped with a mechanical stirrer and thermometer. The reaction
mixture is heated at a temperature of about 85C for a period of about
45 minutes resulting in the formation of a precipitate. After this time
the precipitate is recovered by filtration and dried to yield the de-
sired product 1-(5,7-dimethoxy-4,5,6,7-tetrahydrobenzothiazol-2-yl)-3-ethyl-
5-hydroxy-1,3-imidazolidin-2-one.
Example 11
Preparation of Ethyl N-(5-Ethyl-7-chloro-4,5,6,7-tetrahydro-
benzothiazol-2-yl)carbamate
2-Amino-5-ethyl-7-chloro-4,5,6,7-tetrahydrobenzothiazole (0.10 mol)
dissolved in pyridine (125 ml~ is charged into a glass reaction vessel
equipped with a mechanical stirrer, thermometer and addition funnel.
Ethyl chloroformate (0.12 mol) is then added drop~ise to the reaction
mixture with stirring and cooling. After the addition is completed the
reaction mixture is allowed to warm to room temperature and stirring is
continued for a period of about 1 hour. After this time the reaction
mixture is poured into ice water to form a precipitate. The precipitate
is recovered by filtration, is dried and recrystallized to yield the
25 desired product ethyl N-(5-ethyl-7-chloro-4,5,6,7-tetrahydrobenzothiazol-2-
yl)carbamate.
Example 12
Preparation of the Dimethyl Acetal of 2- ~-All~l-3-
(5-ethyl-7-chloro-4,5,6,7-tetrahydrobenzothiazol-2-yl)-
- ureidQJacetaldehyde
Ethyl N-(5-ethyl-7-chloro-4,5,6,7-tetrahydrobenzothiazol-2-yl)-
carbamate (0.08 mol) and the dimethyl acetal of 2-a Uylaminoacetalde-
hyde (30 ml) are charged into a glass reaction vessel equipped with
-- 10 --
7~
a stirrer, reflux condenser and gas addition tube. The reaction mix-
ture is blanketed with nitrogen gas and is heated at 125 C for a period
of about 8 hours. After this time the reaction mixture is distilled
to remove excess starting material. The residue is purified by elution
chromatography using ethyl acetate as the eluant. The chromatographed
solution is then stripped of solven-t to yield the desired product di-
methyl acetal of 2- ~-allyl-3-(5-ethyl-7-chloro-4,5,6,7-tetrahydrobenzothia-
zol-2-yl)ureid~acetaldehyde.
Example 13
Preparation of 1-(5-Ethyl-7-chloro-4,5,6,7-tetrahydrobenzo-
thiazol-2-yl)-3-allyl-5-hydroxy-1,3-imidazolidin-2-one
The dimethyl acetal of 2-/1-allyl-3-(5,5-diethyl-4,5,6,7-
tetrahydrobenzothiazol-2-yl)ureid ~acetaldehyde (0.05 mol) and dilute
hydrochloric acid (25 ml; 3% conc.) are charged into a glass reaction
vessel equipped with a mechanical stirrer and thermometer. The re-
action mixture is heated at a temperature of about 85 C for a period
of about 45 minutes resulting in the formation of a precipitate.
After this time the precipitate is recovered by Eiltration and dried
to yield the desired product 1-(5-ethyl-7-chloro-4,5,6,7-tetrahydrobenzo-
20 thiazol-2-yl)-3-allyl-5-hydroxy-1,3-imidazolidin-2-one.
Example 14
Preparation of Ethyl ~-(7-Methylthio-4,5,6,7-tetrahydro-
benzothiazol-2-yl)carbamate
2-A~ino-7-methylthio-4,5,6,7-tetrahydrobenzothiazole (0.10 mol)
dissolved in pyridine (125 ml) is charged into a glass reaction vessel
equipped with a mechanical stirrer, thermometer and addition funnel.
Ethyl chloroformate(0.12 mol) is then added dropwise to the reaction
mixture with stirring and cooling. After the addition is completed the
7;~9L
reaction mixture is allowed to warm to room temperature and stirring
is continued for a period of about 1 hour. After this time the re-
action mixture is poured into ice water to form a precipitate. The
precipitate is recovered by filtration, is dried and recrystallized
to yield the desired product ethyl ~-(7-methylthio-4,5,6,7-tetrahydro-
benæothiazol-~-yl)carbamate.
Example 15
Preparation of the Dimethyl Acetal of 2-~ -Chloroethyl-
3-(7-methylthio-4,5,6,7-tetrahydrobenzothiazol-2-yl)-
ureido~acetaldehyde
Ethyl ~-(7-methylthio-4,5,6,7-tetrahydrobenzothiazol-2-yl)-
carbamate (0.08 mol) and the dimethyl acetal of 2-~ -chloroethyl-
aminoacetaldehyde (30 ml~ are charged into a glass reaction vessel
~quipped with a stirrer, reflux condenser and gas addition tube. The
reaction mixture is blanketed with nitrogen gas and is heated at 125 C
for a period of about 8 hours. After this time the reaction mixture
is distilled to remove excess starting material. The residue is puri-
fied by elution chromatography using ethyl acetate as the eluant. The
chromatographed solution is then stripped of solvent to yield the
desired product dimethyl acetal of 2- ~-~ -chloroethyl-3-(7-methylthio-
4,5,6,7-tetrahydrobenzothiazol-2-yl)ureid ~acetaldehyde.
Example 16
Preparation of 1-(7-Methylthio-4,5,6,7-tetrahydrobenzo-
thiazol-2-yl)-3-~ -chloroethyl-5-hydroxy-1,3-imidazoli-
_ din-2-one
The dimethyl acetal of 2- r-~-chloroethyl-3-(7-methylthio-4,5,-
6,7-tetrahydrobenzothiazol-2-yl)ureid ~acetaldehyde (0.05 mol) and dilute
hydrochloric acid (25 ml; 3% conc.) are charged into a glass reaction
- 12 -
~l2~
vessel equipped with a mechanical stirrer and thermometer. The re-
action mixture is heated at a temperature of about 85 C for a period
of about 45 minutes resulting in the formation of a precipitate.
After this time the precipitate is recovered by filtration and dried
to yield the desired product l-(7-methylthio-4,5,6,7-tetrahydroben~o-
thiazol-2-yl)-3-~ -chloroethyl-5-hydroxy-1,3-imidazolidin-2-one.
Example 17
Preparation of Ethyl N-(5-Propyl-7-cyano-4,5~6,7-
tetrahydrobenzothiazol-2-yl)carbamate
2-Amino-5-propyl-7-cyano-4,5,6,7-tetrahydrobenzothiazole
(0.10 mol) dissolved in pyridine (125 ml) is charged into a glass
reaction vessel equipped with a mechanical stirrer, thermometer and
addition funnel. Ethyl chloroformate (0.12 mol) is then added drop-
wise to the reaction mixture with stirring and cooling. After the
addition is completed the reaction mixture is allowed to warm to
room temperature and stirring is continued for a period of about 1 hour.
After this time the reaction mixture is poured into ice water to form
a precipitate. The precipitate is recovered by filtration, is dried
and recrystallized to yield the desired product ethy~N{5-propyl-7-
cyano-4,5,6,7-tetrahydrobenzothiazol-2-yl)carbamate.
Example 18
Preparation of the Dimethyl Acetal of 2-Ll-But-3-enyl-3-
(5-pro~yl-7-cyano-4,5,6,7-tetrahydrobenzothiazol-2-yl)-
ureido~acetaldehyde
Ethyl N-(5-propyl-7-cyano-4,5,6,7-tetrahydrobenzothiazol-2-
yl)carbamate (0.08 mol) and the dimethyl acetal of 2-but-3-enylamino-
acetaldehyde (30 ml) as charged into a glass reaction vessel equippedwith a stirrer, reflux condenser and gas addition tube. The reaction
mixture is blanketed with nitrogen gas and is heated at 125C for a
period of about 8 hours. After this time the reaction mixture is
distilled to remove excess starting material. The residue is purified
by elution chromatography using ethyl acetate as the eluant. The
5 chromatographed solution is then stripped of solvent to yield the
desired product dimethyl acetal of 2-r-but-3-enyl-3-(5-propyl-7-cyano-
4,5,6,7-tetrahydrobenzothiazol-2-yl)ureid~acetaldehyde.
Example 19
Preparation of 1-(5-Propyl-7-cyano-4,5,6,7-tetra-
hydrobenzothiazol-2-yl)-3-but-3-enyl-5-hydroxy-1,3-
imidazolidin-2-one
The dimethyl acetal of 2-r-but 3-enyl-3-(5-propyl-7-cyano-
4,5,6,7-tetrahydrobenzothiazol-2-yl)ureid~acetaldehyde (0.05 mol)
and dilute hydrochloric acid (25 ml; 3% conc.) are charged into a
15 glass reaction vessel equipped with a mechanical stirrer and thermo-
meter. The reaction mixture is heated at a temperature of about 85 C
for a period of about 45 minutes resulting in the formation of a
precipitate. After this time the precipitate is recovered by filtra-
tion and dried to yield the desired product 1-(5-propyl-7-cyano-4,5,6,7-
20 tetrahydrobenzothiazol-2-yl)-3-but-3-enyl-5-hydroxy-1,3-imidazolidin-
2-one.
Example 20
Preparation of Ethyl N-(5-Hexyl-7-propoxy-4,5,6,7-tetrahydro-
benzothiazol-2-yl)carbamate
- 2-Amino-5-hexyl-7-propoxy-4,5,6,7-tetrahydrobenzothiazole
(0.10 mol) dissolved in pyridine (125 ml) is charged into a glass re-
action vessel equipped with a mechanical stirrer, thermometer and
addition funnel. Ethyl chloroformate (0.12 mol) is then added dropwise
- -- 14 --
~I~Z~7~
to the reaction mixture with stirring and cooling. After ~he addition
is completed the reaction mixture is allowed to warm to room temperature
and stirring is continued for a per:Lod of about 1 hour. After this time
the reaction mixture is poured into ice water to form a precipitate.
The precipitate is recovered by filtration, is dried and recrystallized
5 to yield the desired product ethyl N-(5-hexyl-7-propoxy-4,5,6,7-tetra-
hydrobenzothiazol-2-yl)carbamate.
Example 21
Preparation of the Dimethyl Acetal of 2- ~-Propyl-3-(5-hexyl-
7-propoxy-4,5,6,7 tetrahydrobenzothiazol-2-yl)ureido~T-
acetaldehyde
Ethyl ~-(5-hexyl-7-propoxy-4,5,6,7-tetrahydrobenzothiazol 2-
yl)carbamate (0.08 mol) and the dimethyl acetal of 2-propylaminoacetal-
dehyde (30 ml) are charged into a glass reaction vessel equipped with
a stirrer, reflux condenser and gas addition tube. The reaction mixture
15 is blanketed with nitrogen gas and is heated at 125C for a period of
about 8 hours. After this time the reaction mixture is distilled to
remove excess starting material. The residue is purified by elution
chromatography using ethyl acetate as the eluant. The chromatographed
solution is then stripped of solvent to yield the desired product di-
20 methyl acetal of 2-Ll-Propyl-3-(5-hexyl-7-propoxy-4,5,6,7-tetrahydro-
benzothiazol-2-yl)ureidQ~ac~taldehyde.
Example 22
Preparation of 1-(5-Hexyl-7-propoxy-4,5,6,7-tetrahydrobenzo-
thiazol-2-yl)-3-propyl-5-hydroxy-1,3-imidazolidin-2-one
The dimethyl acetal of 2- r-propyl-3-(5-hexyl-7-propoxy-
4,5,6,7-tetrahydrobenzothiazol-2-yl)ureid ~acetaldehyde ( i mol) and
dilute hydrochloric acid (25 ml; 3% conc.) are charged into a glass
~ 15 -
~2~7~9~
reaction vessel equipped with a mechanical stirrer and thermometer. The
reaction mixture is located at a temperature of about 85 C for a period
of about 45 minutes resulting in the formation of a precipitate. After
this time the precipitate is recovered by filtration and dried to yield
the desired product 1-(5-hexyl-7-propoxy-4,5,6,7-tetrahydrobenzothia-
zol-2-yl)-3-propyl-5-hydroxy-1,3-imidazolidin-2-one.
Example 23
Preparation of Ethyl N-(5-Ethylthio-4,5,6,7-tetrahydro-
benzothiazol-2-yl)carbamate
2-Amino-5-ethylthio-4,5,6,7-tetrahydrobenzothiazole (0.10 mol)
dissolved in pyridine (125 ml) is charged into a olass reaction vessel
equipped with a mechanical stirrer, thermometer and addition funnel.
Ethyl chloroformate (0.12 mol) is then added dropwise to the reaction
mixture with stirring and cooling. After the addition is completed
the reaction mixture is allowed to warm to room temperature and stir-
ring is continued for a period of about 1 hour. After this time the
reaction mixture is poured into ice water to form a precipitate. The
precipitate is recovered by filtration,is dried and recrystallized to
; 20 yield the desired product ethyl N-(5-ethylthio-4,5,6,7-tetrahydrobenzo-
thiazol-2-yl)carbamate.
Example 24
Preparation of the Dimethyl Acetal of 2- r-Bromomethyl-3-
(5-ethylthio-4,5,6,7-tetrahydrobenzothiazol-2-yl)ureid~-
acetaldehyde
Ethyl N-(ethylthio-4,5,6,7-tetrahydrobenzothiazol-2-yl)-
carbamate (0.08 mol) and the dimethyl acetal of 2-bromomethylamino-
acetaldehyde (30 ml) are charged into a glass reaction vessel equipped
~ith a stirrer, reflux condenser and gas addition tube. The reaction
- 16 -
7;~
mixture is blanketed with nitrogen gas and is heated at 125C for a
period of about 8 hours. After this time the reaction ~ixture is
distilled to remove excess starting material. The residue is puri-
fied by elution chromatography using ethyl acetate as the eluant.
The chromatographed solution is then stripped of solvent to yield the
desired product dimethyl acetal of 2- r-bromomethyl-3-(5-ethylthio-
4,5,6,7-tetrahydrobenzothiazol-2-yl)ureid ~ acetaldehyde.
Example 25
10 Preparation of 1-(5-Ethylthio-4,5,6,7-tetrahydrobenzothiaæol-
2-yl)-3-bromomethyl-5-hydroxy-1,3-imidazolidin-2-one
The dimethyl acetal of 2- r-bromomethyl-3-(5-ethylthio-4,5,6,7-
tetrahydrobenzothiazol-2-yl)ureid ~acetaldehyde (0.05 mol) and dilute
hydrochloric acid (25 ml; 3% conc.) are charged into a glass reaction
vessel equipped with a mechanical stirrer and thermometer. The re-
action mixture is heated at a temperature of about 85 C for a periodof about 45 minutes resulting in the formation of a precipitate.
After this time the precipitate is recovered by filtration a~d dried to
yield the desired product 1-(5-ethylthio-4,5,6,7-tetrahydrobenzothiazol-
2-yl)-3-bromomethyl-5-hydroxy-1,3-imidazolidin-2-one.
Example 26
Preparation of Ethyl N-(4,5,6,7-Tetrahydrobenzo-
thiazol-2-yl)carbamate
2-Amino-415,6,7-tetrahydrobenzothiazole (0.10 mol) dissolved
in pyridine (125 ml) is charged into a glass reaction vessel equipped
with a mechanical stirrer, thermometer and addition funnel. Ethyl
chloroformate (0.12 mol) is then added dropwise to the reaction mix-
ture with stirring and cooling. After the addition is completed
the reaction mixture is allowed to warm to room temperature and stir-
ring is continued for a period of about 1 hour. After this time the
- 17 -
7;3~
reaction mixture is poured into ice water to form a precipitate. The
precipitate is recovered by filtrat:ion, is dried and recrystallized
to yield the desired product ethyl N-(4,5,6,7-tetrahydrobenzothiazol-
2-yl)carbamate.
Example 27
Preparation of the Dimethyl Acetal of 2- r-Methyl-
3-(4,5,6,7-tetrahydrobenzothiazol-2-yl)ureid ~-
acetaldehyde
Ethyl N-(4,5,6,7-tetrahydrobenzothiazol-2-yl)carbamate
(0.08 mol) and the dimethyl acetal of 2-methylaminoacetaldehyde (30
10 ml) are charged into a glass reaction vessel equipped with a stirrer,
reflux condenser and gas addition tube. The reaction mixture is
blanketed with nitrogen gas and is heated at 125C for a period of
about 8 hours. After this time the reaction mixture is distilled to
remove excess starting material. The residue is purifi~d by elution
15 chromatography using ethyl acetate as the eluant. The chromatographed
solution is then stripped of solvent to yield the desired product
dimethyl acetal of 2- ~-methyl-3-(4,5,6,7-tetrahydrobenzothiazol-2-
yl)ureid ~ace.aldehyde.
Example 28
Preparation of 1-(4,5,6,7-tetrahydrobenzothiazol-2-yl)-
3-methyl-5-hydroxy-1,3-imidazolidin-2-one
The dimethyl acetal of 2- r-methyl-3-(4,5,6,7-tetrahydro-
benzothiazol-2-yl)ureid ~ acetaldehyde (0.05 mol) and dilute hydro-
chloric acid (25 ml; 3% conc.) are charged into a glass reaction
25 vessel equipped with a mechanical stirrer and thermometer. The
reaction mixture is heated at a temperature of about 85C for a
period of about 45 minutes resulting in the formation of a precipitate.
- 18 -
7;~
After this time the precipitate is recovered by filtration and dried
to yield the desired product 1-(4,5,6,7-tetrahydrobenzothiazol-2-yl)-
3-methyl-5-hydroxy-1,3-imidazolidin-2-one.
Additional compounds within the scope of the present in-
5 vention ~hich can be prepared by the methods detailed in the fore-
going examples are:
1-(5-propylthio-4,5,6,7-tetrahydrothiazol-2-yl)-3-~-iodobutyl-
5-hydroxy-1,3-imidazolidin-2-one, 1-(5-butylthio-4,5,6,7-tetrahydrothia-
zol-2-yl)-3-methyl-5-hydroxy-1,3-imidazolidin-2-one, 1-(7-pentylthio- -
4,5,6,7-tetrahydrothiazol-2-yl)-3-butyl-5-hydroxy-1,3-imidazolidin-2-
one, 1-(7-hexylthio-4,5,6,7-tetrahydrothiazol-2-yl)-3-pentyl-5-hydroxy-
1,3-imidazolidin-2-one, 1-(5,7-diethoxy-4,5,6,7-tetrahydrothiazol-2-yl)-
3-hexyl-5-hydroxy-1,3-imidazolidin-2-one, 1-(5-butoxy-4,5,6,7-tetrahydro-
thiazol-2-yl)-3-pent-4-enyl-5-hydroxy-1,3-imidazolidin-2-one, 1-(7-
hexyloxy-4,5,6,7-tetrahydrothiazol-2-yl)-3-hex-3-enyl-5-hydroxy-1,3-
imidazolidin-2-one, 1-(5,7-dibutyl-4,5,6,7-tetrahydrothiazol-2-yl)-3-~-
fluoroethyl-5-hydroxy-1,3-imidazolidin-2-one, 1-(5,5,7-triethyl-4,5,6,7-
tetrahydrothiazol-2-yl)-3-o-chlorohexyl-5-hydroxy-1,3-imidazolidin-2-
one, 1-(5,5,7-trimethyl-7-cyano-4,5,6,7-tetrahydrothiazol-2-yl)-3-
methyl-5-hydroxy-1,3-imidazolidin-2-one, 1-(5-cyano-5,7-dimethyl-4,5,6,7-
tetrahydrothiazol-2-yl)-3-methyl-5-hydroxy-1,3-imidazolidin-2-one, 1-(5-
dimethylamino-4,5,6,7-tetrahydrothiazol-2-yl)-3-methyl-5-hydroxy-1,3-
imidazolidin-2-one, 1-(5-diethylamino-4,5,6,7-tetrahydrothiazol-2-yl)-3-
methyl-5-hydroxy-1,3-imidazolidin-2-one, 1-(7-dibutylamino-4,5,6,7-
tetrahydrothiazol-2-yl)-3-propargyl-5-hydroxy-1,3-imidazolidin-2-one,
1-(5,5,7-trimethyl-4,5,6,7-tetrahydrothiazol-2-yl)-3-propargyl-5-hydroxy-
1,3-imidazolidin-2-one, 1-(5-bromo-4,5,6,7-tetrahydrothiazol-2-yl~-3-
propargyl-5--hydroxy-1,3-imidazolidin-2-one.
- 19 -
~ - , - .. ~ ..
3 ~Z~7;3~
For practical use as herbicides the compounds of this inven-
tion are generally incorporated into herbicidal compositions which com-
prise an inert carrier and a herbicidally toxic amount of such a compound.
Such herbicidal compositions, which can also be called formulations,
enable the active compound to be applied conveniently to the site of the
weed infestation in any desired quantity. These compositions can be
solids such as dusts, granules, or wettable powders; or they can be
liquids such as solutions, aerosols or emulsifiable concentrates.
For example, dusts can be prepared by grinding and blending
the active compound with a solid inert carrier such as the talcs, clays,
silicas, pyrophyllite, and the like. Granular formulations can be pre-
pared by impregnating the compound, usually dissolved in a suitable
solvent, onto and into granulated carriers such as the attapulgites or
the vermiculites, usually of a particle si~e range o from about 0.3 to
1.5 mm. Wettable powders, which can be dispersed in water or oil to any
desired concentration of the active compound, can be prepared by incorpor-
ating wetting agents into concentrated dust compositions.
In some cases the active compounds are sufficiently soluble
in common organic solvents such as kerosene or xylene so that they can
be used directly as solutions in these solvents. Frequently, solutions
of herbicides can be dispersed under super-atmospheric pressure as
aerosols. However, preferred liquid herbicidal compositions are emulsi-
fiable concentrates, which comprise an active compound according to
this invention and as the inert carrier, a solvent and an emulsifier.
Such emulsifiable concentrates can be extended with water and/or oil
to any desired concentration of active compound for application as sprays
to the site of the weed infestation. The emulsifiers most commonly
used in these concentrates are nonionic or mixtures of nonionic with
anionic surface-active agents. ~ith the use of some emulsifier systems
an inverted emulsion twater in oil) can be prepared for direct application
- 20 -
.
, ., . , ~ ~,.. .. ....
~2~i73~
to weed infestations.
A typical herbicidal composition according to this invention
is illustrated by the following exal~ple, in which the quantities are
in parts by weight.
Examp:Le 29
Preparation of a Dust
Product of Example 10
Powdered Talc 90
The above ingredients are mixed in a mechanical grinder-blender
and are ground until a homogeneous, free-flowing dust of the desired
particle size is obtained. This dust is suitable for direct application
to the site of the weed infestation.
The compounds of this invention can be applied as herbicides
in any manner recognized by the art. One method for the control of weeds
comprises contacting the locus of said weeds with a herbicidal composi-
tion comprising an inert carrier and as an essential active ingredient,
in a quantity which is herbicidally toxic to said weeds, a compound of
the present invention. The concentration of the new compounds of this
invention in the herbicidal compositions will vary greatly with the
type of formulation and the purpose for which it is designed, but
generally the herbicidal compositions will comprise from about 0.05 to
about 95 percent by weight of the active compounds of this invention.
In a preferred embodiment of this invention, the herbicidal compositions
will comprise from about 5 to about 75 percent by weight of the active
compound. The compositions can also comprise such additional substances
as other pesticides, such as insecticides, nematocides, fungicides,
and the like; stabilizers, spreaders, deactivators, adhesives, stickers,
fertilizers, activators, synergists and the like.
- 21 ~
;73~
The compounds o~ 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% to about
95% of the active ingredients in the herbicidal compositions. Use of
combinations of 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
provide results unattainable with separate compositions of the individ-
ual herbicides. The other herbicides, defoliants, dessicants and plant~rowth inhibitors, with which the compounds of this invention can be
used in the herbicidal compositions to control weeds, can include
chlorophenoxy herbicides such as 2,4-D, 2,4,5-T, ~ICPA, ~CPB, 4(2,4-DB),
2,4-DEB, 4-CPB, 4-CPA, 4-CPP, 2,4,5-TB, 2,4,5-TES, 3,4-DA, silvex and
the like; carbamate herbicides such as IPC, CIPC, swep, barban, BCPC,
CEPC, CPPC, and the like; thiocarbamate and dithiocarbamate herbicides
such as CDEC, metham sodium, EPTC, diallate, PEBC, perbulate, vernolate
and the like; substituted urea herbicides such as norea, siduron,
dichloral urea, chloroxuron, cycluron, fenuron, monuron, monuron TCA,
~0 diuron, linuron, monolinuron, neburon, buturon, trimeturon and the like;
symmetrical triazine herbicides such as simazine, chlorazine, atraone,
desmetryne, norazine, ipazine, prometryn, atrazine, trietazine, simetone,
prometone, propazine, ametryne, and the like; chloroacetamide herbicides
such as alpha-chloro-N,N-dimethylacetamide, CDEA, CDAA, alpha-chloro-
~-isopropylacetamide, 2-chloro-N-isopropylacetanilide, 4-(chloroacetyl)-
morpholine, l-(chloracetyl)piperidine, and the like; chlorinated aliphatic
acid herbicides such as TCA, dalapon, 2,3-dichloropropionic acid, 2,2,3-
TPA and the Like; chlorinated benzoic acid and phenylacetic acid herbicides
- 22 -
~.Z~3~
such as 2,3,6-TBA, 2,3,5,6-TBA, dicamba, tricamba, amiben, fenac,
PBA, 2-methoxy-3,6-dichlorophenylacetic acid, 3-methoxy-2,6-dichloro-
phenylacetic acid, 2-methoxy-3,5,6-trichlorophenylacetic acid, 2,4-
dichloro-3-nitrobenzoic acid and the like; and such compounds as amino-
triazole, maleic hydrazide, phenyl mercuric acetate, endothal, biuret,technical chlordane, dimethyl 2,3,5,6-tetrachloroterephthalate, diquat,
erbon, DNC, D~BP, dichlobenil, DPA, diphenamid, dipropalin, trifluraline,
solan, dicryl, merphos, DMPA, DSMA, MSMA, potassium azide, acroleln,
benefin, bensulide, AMS,bromacil, 2-(3,4-dichlorophenyl)-4-methyl-1,2,4-
oxadiazolidine-3,5-dione, bromoxynil, cacodylic acid, CMA, CPMF, cypro-
mid, DCB, DCPA, dichlone, diphenatril, DMTT, DNAP, EBEP, EXD, HCA,
- ioxynil, IPX, isocil, potassium cyanate, MAA, MAMA, MCPES, MCPP, MH,
~olinate, NPA, OCH, paraquat, PCP, picloram, DPA, PCA, pyrichlor,
sesone, terbacil, terbutol, TCBA, brominil, CP-50144, H-176-1, H-732,
M-2901, planavin, sodium tetraborate, calcium cyanamid, DEF, ethyl
xanthogen disulfide, sindone, sindone B, propanil and the like.
Such herbicides can also be used in the methods and composi-
tion of this invention in the form of 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 economic value, and interfering with the production of cul-
tivated crops, with the growing of ornamental plants, or with the wel-
fare of livestock. Many types of weeds are known, including annuals
such as pigweed, lambsquarters, foxtail, crabgrass, wild mustard, field
pennycress, ryegrass, goose-grass, chickweed,wild oats, velvet leaf,
purselane, barnyard grass, smartweed, knotweed, cocklebur, wild buck-
wheat, kochi.a, medic, corn cockle, ragweed, sowthistle, coffee-weed,
croton, cuphea, dodder, fumitory, groundsel, hemp nettle, knowel, spurge,
spurry, emex, jungle rice, pondweed, dog fennel, carpetweed, morning
- 23 -
1~2~7;~9~
glory, bedstraw, ducksalad and naiad; biennials such as wild carrot,
matricaria, wild barley, campion, chamomile, burdock, mullein, round-
leaved mallow, bull thistle, hounds-tongue, moth mullein, and purple
star thistle; or perennials such as white cockle, perennial rye-grass,
quackgrass, Johnson grass, Canada thistle, hedge bindweed, Bermuda
grass, sheep sorrel, curly dock, nutgrass, field chickweed, dandelion,
campanula, field bindweed, Russian knapweed, mesquite, toadflax, yarrow,
aster, gromwell, horsetail, ironweed, sesbania, bulrush, cattail and
winter-cress.
Similarly, such weeds can be classified as broadleaf or grassy
weeds. It is economically desirable to control the growth of such
weeds without damaging beneficial plants or livestock.
The new compounds of this invention are particularly valuable
for weed control because they are toxic to many æpecies and groups of
weeds while they are relatively nontoxic to many beneficial plants.
The exact amount of compound required will depend on a variety of
factors, including the hardiness of the particular weed species,
weather, type of soil, method of application, the kind of beneficial
plants in the same area, and the like. Thus, while the application
of up to only about one or two ounces of active compound per acre
may be sufficient for good control of a light infestation of weeds
growing under adverse conditions, the application of ten pounds or
more of active compound per acre may be required for good control of
a dense infestation of hardy perennial weeds growing under favorable
conditions.
The herbicidal toxicity of the new compounds of this invention
can be illustrated by many of the established testing techniques known
to the art, such as pre- and post- emergence testing.
The herbicidal activity of the compounds of this invention
- 24 -
~Z~7~
was demonstrated by experiments carried out for the pre-emergence
control of a variety of weeds. In these experiments small plastic
greenhouse pots filled with dry soil were seeded with the various
weed seeds. Twenty-four hours or less after seeding,the pots were
sprayed with water until the soil was wet and the test compounds
formulated as aqueous emulsions of acetone solutions cantaining emul-
sifiers were sprayed at the indicated concentrations on the surface
of the soil.
After spraying, the soil containers were placed in the green-
house and provided with supplementary heat as required and daily or
more frequent watering. The plants were maintained under these condi-
tions for a period of from 15 to 21 days, at which time the condition
of the plants and the degree of injury to the plants was rated on a
scale of from 0 to 10, as follows: 0 = no injury, 1,2 = slight injury,
~5 3,4 = moderate injury, 5,6 = moderately severe injury, 7,8,9 = severe
injury and 10 = death. The effectiveness of these compounds is demon-
strated by the following data set out in Tables I and II. Numbers
with decimal places are the result of averaging two or more ratings
obtained from replicate experiments.
The herbicidal activity of the compounds of this invention
was also demonstrated by experiments carried out for the post-emergence
control of a variety of weeds. In these experiments the compounds to
be tested were formulated as aqueous emulsions and sprayed at the
` indicated dosage on the foliage of the various weed species that have
attained a prescribed size. After spraying,the plants were placed
in a greenhouse and watered daily or more frequently. Water was not
applied to the foliage of the treated plants. The severity of the
injury was determined 10 to 15 days after treatment and was rated on
the scale o~ from 0 to 10 heretofore described. The effectiveness of
- 25 -
~ 2S,7;~
these compounds is demonstrated by the following data set forth in
Tables III and IV. Values with decimal places again are the result
of averaging of replicate experimerlts.
- 26 -
i73~
TABLE I - PRODUCT OF EXAMP~E 4
Pre-emergence: Injury Rating
Concentration - lbs/acre
Weed Species8.02.01.00.50.250.125
Yellow Nutsedge 500.0
Wild Oats10106.75.02.51.0
Jimson~eed101010.0 - 4.05.0
Velvetleaf10109.08.510.08.5
Johnsongrass9107.76.52.52.0
Pigweed997.03.51.51.0
Wild Mustard101010.010.010.04.0
Yellow Foxtail 1087.05.52.01.5
Baruyardgrass 10109.310.07.00.0
Crabgrass988.07.03.01.5
Cheatgrass1097.05.03.50.5
Morningglory8108.37.04.04.5
Birdweed - -10.05.03.01.5
O~uackgrass - -5.54.54.02.5
Sprangletop - -10.09.04.53.5
Pintobeau - -9.56.53.02.5
Sugarbeet - -9.08.58.09.5
Wheat - -9.58.07.52.5
Rice - -4.03.53.02.0
Soybean - -6.54.01.01.0
Cotton - -10.05.02.50.5
Sorghum - -10.010.05.04.5
Corn _ _70553005
Alfalfa - -10.03.52.01.0
Oa~ - -6.52.52.01.0
, ~ , . . . . .
l~;Zfi73~
-TABLE II - PRODUCT OF EXAMPLE 7
Pre-emergence: Injury Rating
Concentration - lbs/acre
Need Species 2.01.00.50.250.125
Yellow Nutsedge 3.00.00.0
Wild Oats10.09.32.70.0 0.0
Jimsonweed10.04.02.54.0 1.0
Velvetleaf10.010.08.55.5 1.0
Johnsongrass10.06.53.20.0 0.0
Pigweed 10.06.03.50.0 0.0
Nild ~lustard10.09.010.01.0 0.5
Yellow Foxtail 9.06.72.20.5 0.5
Barnyardgrass10.05.75.22.0 1.0
Crabgrass6.04.51.71.5 2.0
Cheatgrass10.06.71.70.5 0.0
Morningglory10.07.68.45.0 1.5
Birdweed - 10.05.53.0 0.0
Cocklebur7.02.01.00.0
Quackgrass -10.06.02.5 0.0
Sprangletop -5.02.50.0 0.0
Pintobeau -6.03.00.0 0.0
Sugarbeet -10.010.08.0 6.0
Wheat -9.55.51.5 1.0
Rice -4.02.53.5 0.0
Soybean 6.03.70.70.3 1.0
Cotton 2.01.70.00.0 0.0
Sorghum -10.04.02.0 1.0
Corn -3.00.50.0 0.0
Alfalfa -5.00.00.0 0.0
Oat -4.00.00.0 0.0
- 28 -
~Z~7;;~
ABLE III - PRODUCT OF E~AMPLE 4
Post-emergence: Injury Rating
Concentration - lbs/acre
Weed Species2.0 1.0 0.5 _0.25 0.125
Wild Mustard 10.0 10.0 10.0 10.0 10.0
Wild Oat 10.0 3.5 4.0 2.0 1.0
Bindweed 10.0:LO.0 10.0 10.0 3.0
Barnyardgrass10.0 10.0 10.0 10.0 5.0
Crabgrass 9.0 9.5 9.5 10.0 10.0
Yellow Foxtail9.0 10.0 10.0 6.0 4.0
Johnsongrass 10.0 9.5 8.0 3.0 2.0
Morningglory 10.0 10.0 10.0 10.0 10.0
Jimsonweed 10.0 10.0 10.0 10.0 5.0
Yellow ~utsedge 5.0 2.0 2.0
Pigweed 10.0 10.0 10.0 10.0 10.0
Velvetleaf - 10.0 10.0 10.0 10.0
Quackgrass - 10.0 6.0 4.0 2.0
Sprangletop - 10.0 10.0 4.0 3.0
Cheatgrass - 10.0 10.0 2.0 2.0
Pintobeau - 10.0 10.0 10.0 10.0
Sorghum - 10.0 10.0 10.0 10.0
Wheat - 10.0 5.0 10.0 1.0
Rice - 5.0 4.0 4.0 2.0
Cotton - 10.0 10.0 10.0 10.0
Corn - 7.0 10.0 4.0 3.0
~Lfalfa - 10.0 10.0 10.0 10.0
Oat - 2.0 2.0 0.0 0.0
Soybean - 10.0 10.0 10.0 10.0
Sugarbeet - 10.0 10.0 10.0 10.0
- 29 -
~ ~;.;Z6~
TABLE IV - PRODUCT OF EXAMPLE 7
Post-emergence: Injury Rating
Concentration - lbs/acre
Weed Species2.0 1.0 0.5 0.25 0.1250.062
Nild Mustard10.010.0 10.0 10.0 6.5 2.0
Wild Oat 10.0 5.0 2.0 0.0 0.0 0.0
Bindweed 10.010.0 9.0 5.5 1.0 0.0
Barnyardgrass 10.0 10.0 7.2 6.0 3.5 2.0
Crabgrass 10.0 8.7 6.2 4.5 2.0 0.0
Yellow Foxtail 10.0 5.7 5.7 2.5 1.0 0.0
Johnsongrass10.08.0 6.0 5.5 3.5 5.0
Morningglory10.010.0 10.0 6.5 10.0 5.0
Jimsonweed 10.0 9.3 9.2 8.5 8.510.0
Yellow Nutsedge 2.0 0.5 0.0
Pigweed 10.0 8.3 7.5 6.0 4.0 3.0
Velvetleaf - 10.0 10.0 10.0 8.5 7.0
0~uackgrass - 10.0 10.0 7.0 2.0 2.0
Sprangletop - 10.0 6.0 5.5 1.0 0.0
Cheatgrass - 10~0 5.0 5.0 0.0 0.0
Pintobeau - 5.0 10.0 7.0 7.0 3.0
Sorghum - 10.0 5.0 1.0 1.0 0.0
Wheat - 2.0 1.5 1.0 0.0 0.0
Rice - 7.0 5.5 10.0 0.5 0.0
Cotton - 10.0 10.0 8.5 7.510.0
Corn - 4.0 3.0 0.5 0.5 0.0
Alfalfa - 10.0 10.0 9.5 9.5 4.0
Oat - 2.0 0.5 1.0 0.5 0.0
Soybean 10.010.0 7.0 4.5 3.5 3.0
Sugarbeet - 10.0 10.0 8.5 6.5 2.0
- 30 -
