Note: Descriptions are shown in the official language in which they were submitted.
~%~6589
-- 1 --
HERBICIDAL l-ARYL-~-1,2,4-TRIAZOLIN-5-ONES
The invention described in this application
pertains to weed control in agriculture, horticulture,
or other fields where there is a desire to control
5 unwanted plant growth. More specifically, the present
application describes novel herbicidal l-ary~2-
1,2,4-triazolin-5-ones, herbicidal composi~ions
containing ~he new compounds, methods for preparing
the compounds, and methods for preYenting or
10 destroying undesired plant growth by preemergence or
post-emergence application of the herbicidal
compositions to the locus where control is desired.
The present compounds may be used to effectively
control a variety of both grassy and broadleaf plant
species. The present invention is particularly useful
in agriculture, as the novel aryltriazolinones
described herein show a selectivity favorable to
cotton or other crops at application levels which
inhibit the growth o~ or destroy a variety of weeds.
Various herbicidal l^aryl-A2-1,2,4-triazolin-
5-ones are known in the art. U.S. Patent No.
4,318,731 and corresponding British Patent No.
2,056,971 disclose herbicidal aryltriazolinones of the
formula
Cl O
Cl~
wherein Rl is alkyl, ~2 is hydrogen, alkyl, or
alkenyl, and X is hydroxy, alkyl, alkoxy, alkoxy-
alkoxy, alkenyloxy, or alkyloxycarbonylalkyloxy.
British Patent No. 2,090,250, adds to the above
:
" ,, ,.,~
12~658~
,
genus compounds wherein R2 is alkynyl, halomethyl,
or haloethyl, and X is alkoxy, alkenyloxy, alkynyloxy,
alkoxyalkoxy,`hydroxy, halomethyloxy, or haloethyloxy.
European Patent Application Publication No. 55,105
discloses a series of herbicidal aryltriazolinones of
the formula
F O
~N
wherein R is alkyl, alkenyl, or cycloalkyl, X is
lS chlorine or bromine, and Y is hydrogen or alkoxy.
Japanese Kokai 81-32,468 discloses herbicidal
aryltriazolinones of the formula
Cl o
Cl J~' ~
wherein R is hydrogen, alkyl, or 2-propenyl, and
is methyl or alkoxy.
South African Patent Application No. 78/3182
discloses herbicidal aryltriazolinones of the formula
Rn ~ ~ - Rl
wherein Rn is hydrogen or represents 1 to 4 same or
different radicals selected from halogen, nitro,
cyano, optionally halo substituted alkyl, alkoxy, or
s~9
alkylthio, and optionally substituted phenyl or
phenoxy, an~ Rl is alkyl5 alkoxyalkyl, dialkoxy-
ethyl, dialkylaminoethyl, or cycloalkyl.
U.S. Patent No. 4,315,767 discloses herbicidal
bicyclic compounds of the following formula
. Y Q
lo J~,~ ( C~2~n
wherein V is hydrogen, halogen, methyl, or alkoxy> X
is hydrogen, halogen, cyano, methyl, methoxy, or
nitro, Y is hydrogen, halogen, or methyl, m and n are
0 to 4 (m plus n is 2 to 4), Q is oxygen or sulur,
and Z is oxygen, S(O)p, or NRl wherein p is 0-2
and R is alkyl, provided that when m plus n is 2 or
4 then Y and X are other than hydrogen, and .when Z is
S(O)p then n is 1 to 4.
Additional herbicidal bicyclic compounds based on
the aryltriazolinone nucleus are disclosed in U.S.
Patent No. 4,213,773 and have the following structural
formula
Y Q
~ Nf--~
(CH2~n
tCH3)m
wherein V is hydrogen, halogen, hydroxy, alkyl, or
-ORl; Rl is optionally substituted alkyl,
cycloalkyl, cycloalkylalkyl, optionally substituted
alkenyl, alkynyl, optionally substituted benzyl,
alkylaminocarbonyl, (alkyl)(methyl or methoxy)amino-
carbonyl, acyl, alkoxycarbonyl, or -CHR7R8 wherein
R7 is hydrogen or alkyl and :R8 is cyano, acetyl,
~24~589
-- 4
hydroxycarbonyl, alkoxycarbonyl~ hydroxymethyl,
alkoxymethyl, alkylcarbonyloxymethyl, hydroxycarbonyl-
ethenyl, alkoxycarbonylethenyl, or a group
-CO-NRllR12 wherein Rll is hydrogen, alkyl,
alkenyl, or alkoxy, and R12 is hydrogen or alkyl; X
is halogen, cyano, methyl, methoxy, or nitro; Y is
hydrogen, halogen, or methyl; Z is hydrogen or
halogen; n is 3-5; m is 0-2; and Q is oxygen or
sulfur, ~ith certain provisos.
A class of ~2-1,2,4-triazolin-5-ones is
disclosed as fungicides in U.S. 4,~98,896. The
disclosed genus has the formula
~1_ S ~ ~ R
N 1~ 2
SR
wherein R is alkyl, alkenyl, alkynyl, cycloalkyl, or
optionally substituted phenyl or arylalkyl, Rl is
haloalkyl or haloalkenyl, and R is optionally sub-
stituted alkyl, alkenyl, or alkynyl, or optionally
substituted aryl, arylalkyl, or alkylaryl.
The compounds of this invention are 1-~4-chloro-
2-fluoro-5-(substituted)oxyphenyl]-3-methyl-4-
difluoromethyl-~2-1,2,4-triazolin-5-ones of the
formula
Cl ~ - CHF2 I
P~C) CH 3
wherein R is alkyl, alkenyl, alkynyl, alkoxyalkyl, or
alkyl S~O)n-alkyl wherein n is 0 to 2.
, . . .
-
iL2~5~
-- 5
The present compounds are named in accordance wi~h
the numbering system shown in formula I, for the ring
atoms of the heterocycle which is the same as ~he
numbering system used in V.S. 4,318,731, supra, for
5 similar compounds.
A preferred embodiment of this invention is 1-(4-
chloro-2-fluoro-~ propargyloxyphenyl)-3-methyi-4-
difluoromethyl-~2-1,2,4-triazolin-5-one, the
compound oE the formula
F
Cl ~ CHF2 ~a)
~C_CCH20 CH3
Other pre~erred embodiments include the compounds
of formula I in which R is -CH3, -CH(CH3)2, -CH(C~3)C-CH,
-CH20CH3, -CH2CH=CH2, and -CH(CH3)CH2OCH3-
The present compounds, which have a fluorine atom
20 at the C-2 position of the phenyl ring, in ~eneral
have herbicidal properties far superior to those of
the correspondin~ compounds having a chlorine atom at
C-2 of the phenyl ring, and are highly active at low
application rates against a variety of grassy and
25 broadleaf weed species in both preemergence and
postemergence applications.
The compounds of this invention may be prepared by
methods analogous to the methods described in the
references above for similar co~pounds or by methods
30 within the skill of the art. A method of preparation
exemplified herein is illustrated in the following
chemical equations for the compound of formula I(a).
j
- ~2~i5~3~
Cl NaN02/HC1 C1
C~30~ F sncl2-2EJ2o/Elc~ H3CO--~ F
NH2 ~5 to 09C NHNH2
II III
.
C1 ,,
III ~ Cll CCOOII lOX HClH3Co--~ F
EtOH
40C NH-N=&CH
IV CH3
IV (00)2P(O)N3 ~ Cl ~
~CH3 OC~3 C113
re1ux V
CHC1F2 F ~ o
NaOII/TlSAB ~ Cl~ N~N CHF2
cyclohexane 0 3 N 1~
ref 1ux CH3
VI
VI CH2C12 ~ C1--~ Nh~CHF2
10C OH CH3
VII
P O
~rClt2(:_(:11 ~ ~11
VII ~C2C03 ~ Cl~ CH1~`2
ref luxF ` OCH2C-CH C~13
I(~,~
65~3~
Optionally, the propargyloxy group, also known as
2-propynyloxy, may be added at an earlier stage in the
synthesis rather than in the last step: for example,
at the outset by using 4-chloro-2-fluoro-5-propar-
5 gyloxyaniline as the starting material in place ofcompound II (the corresponding ~-methoxy compound).
4-Chloro-2-fluoro-5-methoxyaniline, compound II, was
prepared in five steps from commercially available
2-chloro-4-fluorophenol in a known manner (see E.
10 Nagano et al. in European Patent Application
Publication No. 69,855, published January 19, 1983).
Compound II was converted to the corresponding
hydrazine III by diazotization followed by reduction
of the diazonium salt with stannous chloride.
Treatment oE the arylhydrazine with pyruvic acid in
the presence of 10% hydrochloric acid and ethanol gave
the arylhydrazone IV which upon treatment with
diphenylphosphoryl azide afforded the aryltriazolinone
V. Compound V was converted to the present compound
- ~o I(a) in three steps by methods analo~ous to those
disclosed in British Patent No. 2,090,250 for similar
compounds; this conversion is exemplified herein in
Example 1 steps D and E and Example 2. Alkylation of
Compound V with chlorodifluoromethane produced the
N-difluoromethyl derivative VI which was demethylated
at the ether linkage upon treatment with boron
tribromide in methylene chloride to give the
corresponding phenol VII. Alkylation of the
5-hydroxyphenyl compound with propargyl bromide in the
presence of potassium carbonate and acetone produced
the present compound.
Preparation of the present compounds and the
intermediate compounds shown in the chemical equations
abo~e is illustrated further in the following
examples. All temperatures shown are in degrees
Celsius, and reduced pressures for concentration of
- 8 - ~ 5~
liquid were produced by a vacuum pump.
Example 1
PREPARATION OF INTERMEDIATES AND l-(4-CHLORO-2-FLUORO-
5-METHOXYPHENYL)-3-METHYL-4-DIFLUORO-MET~YL-~2-1,2,4-
TRIAZOLIN-5-ONE
A. 4-Chloro-2-fluoro-5-methoxyphenylhydrazine
A stirred solution of 48.0 g (0.27 mole) of 4-
chloro-2-fluoro-5-methoxyaniline in 50 mL of con-
centrated hydrochloric acid was cooled to -5~C, and
23.5 g (0.34 mole) of sodium nitrite in 100 mL of
water was added dropwise. Upon complete addition,
the reaction mixture was stirred at 0C for one hour~
A solution of 154.0 g (0.68 mole) of stannous chlor-
ide in 225 mL of concentrated hydrochloric acid was
cooled to 0C, and the cold solution prepared above
was slowly added to it. Upon complete addition, the
reaction mixture was allowed to warm to ambient
temperature, then was ~iltered to collect a solid.
The solid was made basic and extracted with toluene.
The toluene layer was separated and dried over mag-
nesium sulfate, then filtered. The filtrate was
concentrated under reduced pressure to give 22.4 g of
4-chloro-2-fluoro~5-methoxyphenylhydrazine as a solid.
The nmr spectrum was consistent with the proposed
structure.
B. Pyruvic acid, 4-chloro-2-fluoro-5-methoxyphenyl-
hydrazone
A stirred solution of 21.0 g (0.11 mole) of 4-
chloro-2-fluoro-5-methoxyphenylhydrazine and 100 mL
of aqueous 10% hydrochloric acid in 100 mL of ethanol
was warmed to 40C, and a solution of 10.0 g (0.114
mole) of pyruvic acid in 20 mL of water was added.
Upon complete addition, the reaction mixture was
stirred for one hour. An additional 50 mL of water
was added, and the reaction mixture was filtered to
collect a solid. The solid was air dried to give 29.0
g of pyruvic acid, 4-chloro-2-fluoro-5 methoxyphenyl-
i58~
g
hydrazone; mp 166-169C.
The nmr spectrum was consistent with the proposed
structure.
C. 1-(4-Chloro-2-fluoro-5-methoxyphenyl)-3-methyl-
5 ~2-1,2,4-triazolin-5-one.
A stirred solution of 27.0 g (0.104 mole) of
pyruvic acid, 4-chloro-2-fluoro-5-methoxyphenyl-
hydrazone, 29.0 g (0.105 mole) of diphenylphosphoryl
azide, and 11.0 g ~0.108 mole) of triethylamine in 500
10 mL of toluene was heated under reflux for four hours.
The reaction mixture was cooled to ambient temperature
and extracted with aqueous 10% sodium hydroxide. The
aqueous lay~r was separated and neutralized with
gaseous carbon dioxide, and a solid was collected by
15 filtration. The solid was air-dried to give 11.0 g of
1-(4-chloro-2-fluoro-5-methoxyphenyl)-3-methyl-~2-
1,2,4-triazolin 5-one; mp 193-195C~
The nmr spectrum was consistent with the proposed
structure.
20 D. 1-(4-Chloro-2-fluoro-5-methoxyphenyl)-3-methyl-4-
difluoromethyl-~2-1,2,4-triazolin-5-one.
A stirred mixture of 10.0 g (0.~39 mole) of 1-(4-
chloro-2-fluoro-5-methoxyphenyl)-3-methyl-A2-1,2,4-
triazolin-5-one, 10.0 g (0.031 mole) of tetrabutyl-
25 ammonium bromide, and 10.0 g (0.25 mole) of sodiumhydroxide in 250 mL of cyclohexane was warmed to 60C,
and 10.0 g (0.116 mole) of chlorodifluoromethane was
bubbled into the reaction mixture. Upon complete
addition, the reaction mixture was warmed to reflux
30 temperature and stirred for one hour. The hot solu-
tion was decanted from a pot residue and was allowed
to cool to ambient temperature. Methylene chloride
was added to the cooled mixture to dissolve a solid
precipitate, and the whole was washed with aqueous 10%
35 hydrochloric acid, then with aqueous 10% sodium
hydroxide. The organic layer was separated and dried
1~6589
- 10 -
over magnesium sulfate, then filtered. The filtrate
was concentrated under reduced pressure to give 5.0 g
of 1-(4-chloro-2-fluoro-5-me~hoxyphenyl)-3-methyl-
4-difluoromethyl-~2-1,2;4-triazolin-5-one, mp
5 86-88C.
The nmr spectrum was consistent with the proposed
structure.
E. 1-(4-Chloro-2-fluoro-5-hydroxyphen~ 3-methyl-4-di-
fluoromethyl-~2-1,2,4-triazolin-5-one.
A stirred solution of 4.6 g (0.015 mole) of 1-
(4-chloro-2-fluoro-5-methoxyphenyl)-3-methyl-4-difluoro-
methyl-~2-1,2,4-triazolin-S-one in 200 mL of
methylene chloride was cooled to 10G, and a solution
of 11.2 g (0.045 mole) of boron tribromide in 45 mL of
15 methylene chloride was added. Upon complete addition,
the cooling bath was removed, and the reaction mixture
was stirred for four hours as it warmed to ambient
temperature. Water (100 mL) was added and stirring
was continued for an additional 18 hours. The organic
20 layer was separated, dried over magnesium sulfate, and
filtered. The filtrate was concentrated under reduced
pressure to give 4.4 g of 1-(4-chloro-2-fluoro-5-
hydroxyphenyl-3-methyl-4-difluoromethyl-~2-1,2,4-
triazolin-S-one; mp 147-152C.
The nmr spectrum was consistent with the proposed
structure.
Fxample 2
PREPARATION OF 1-(4-CHLORO-2-FLUORO-5-
PROPARGYLOXYPHENYL)-3-METHYL-4-~IFLUOROMETHYL-
2 ~,4-TRIAZOLIN-5-ONE _ _
To a stirred mixture of 0.7 g t0.0023 mole) of
1-(4-chloro-2-fluoro-5-hydroxyphenyl)-3-methyl-4-di-
fluoromethyl-~2-1,2,4-triazolin-5-one and 0.2 g
35 (0.0015 mole) of potassium carbonate in 50 ~L of
acetone was added 0.3 g (0.0025 mole) of propargyl
- ~2~6S~g
bromide. Upon complete addition, the reaction mixture
~as heated at reflux for three hours, then concentrat-
ed under reduced pressure. The residue was dissolved
in methylene chloride and washed with water and
aqueous 10% sodium hydroxide. The ~r~anic layer was
dried over magnesium sulfate and filtered. The
filtrate was concentrated under reduced pressure to
give 0.33 g of 1-~4-chloro-2-fluoro-5-propar-
gyloxyphenyl)-3-methyl-4-difluoromethyl-~ -1,2,4-
triazolin-5-one as an oil. A sample of this material
was employed in the herbicidal efficacy tests
described below.
The nmr spectrum was consistent with the proposed
structure.
The reaction above was repeated with a purer
sample of 1-(4-chloro-2-fluoro-5-hydroxyphenyl)-
3-methyl-4-difluoromethyl-Q2-1,2,4-triazolin-5-one
(mp 158- 162C) to give the desired propargyloxy
derivative as a solid, mp 75 78C.
The nmr spectrum was consistent with the proposed
structure.
A sample of product prepared in a similar manner
was purified for microanalysis, mp 82-85~C.
Analysis for C13H9ClF3N32
Calc'd: C 47.07, H 2.73, N 12.67;
Found: C 46.86, H 2.47, N 12.48.
Example 3
PREPARATION OF 1-[4-CHLORO-2-FLUORO-5-(1-
MET~YLETHOXY)PHENYL]-3-METHYL-4-DIFLUOROMETHYL-
Q -1,2,4-TRIAZOLIN-5-ONE
.
This compound was prepared in a manner analogous
to Example 2 using 0.50 g (0.0017 mole) of
1-(4-chloro-2-fluoro-5-hydroxyphenyl)-3-methyl-4-di-
fluoromethyl-Q -1,2,4-tria~olin-5-one, 0.36 g
(0.0021 mole) of 2-iodopropane, and 0.71 g (0.0051
mole) of potassium car~onate in 50 mL of acetone. The
2~Sl5 ~
- 12 -
yield of 1-[4-chloro-2-fluoro-5-(1-methylethoxy)-
phenyll-3-methyl-4-difluoromethyl -a 2-1,2,4-triazolin-
5-one was 0.40 ~; m.p. 77-79C.
The nmr spectrum was consistent with the proposed
structure.
Example 4
- PREPARATION OF 1-[4-CHLORO-2-FLUORO-5-
(l-METHYL-2-PROPYNYLOXY)PHENYL]-3-METHYL-4-
DIFLUOROMETHYL-~2-1 2 4-TRIAZOLIN-5-ONE
,
This compound was prepared in a manner analogous
to Example 2 using 05.0 g (0.0017 mole) of
1-(4-chloro-2-fluoro-5-hydroxyphenyl)-3-methyl-4-di-
fluoromethyl-a2-1,2,4-triazolin-5-one, 0.28 g
(0.0021 mole) of 3-bromo-1-butyne, and 0.36 g (0.0021
15 mole) of potassium carbonate in 50 mL of acetone. The
yield of 1-[4-chloro-2-fluoro-5-~1-methyl-2-propynyl-
oxy)phenyl]-3-methyl-4-difluoromethyl ~2-1,2,4-
triazolin-5-one, as an oil, was 0.35 g.
The nmr spectrum was consistent with the proposed
20 structure.
y is for Cl4HllClF3N32
Calc'd: C 48.64, H 3.21, N 12.15;
Found: C 48.39j H 3.32, N ll.9S.
Example 5
PREPARATION OF 1-(4-CHLORO-2-FLUORO-5-METHOXYMETH-
OXYPHENYL)-3-METHYL-4-DIFLUOROMETHYL-~2-1,2,4-
TRIAZOLIN-5-ONE
This compound was prepared in the manner of
Example 2 using 0.75 g (0.0026 mole) of 1-(4-chloro-
30 2-fluoro-5-hydroxyphenyl)-3-methyl-4-difluoromethyl-
-1,2,4-triazolin-5-one, 0.21 g ~0.026 mole) of
chloromethyl methyl ether, and 0.35 g (0.0026 mole) of
potassium carbonate in 60 mL of acetone. The yield of
1-(4-chloro-2-fluoro-5-methoxymethoxyphenyl)-
35 3-methyl-4-difluoromethyl-a2-1,2,4-triazolin-5-one,
as an oil, was 0.84 g.
~2~5~9
- 13 -
The nmr spectrum was consistent with the proposed
structure.
y s for C12HllClF3N33
Calc'd: C 42.68, H 3.28, N 12.44;
Found: C 42.59, H 3.42, N 12.33.
Example 6
PREPARATION OF 1-(4-CHLORO-2-FLUORO-5-ALLYL-
OXYPHENYL)-3-METHYL-4-DIFLUOROMETHYL-~2-1,2,4-
TRIAZOLIN-5-ONE
This compound was prepared in the manner of
Example 2 using 0.75 g (0.0026 mole) of 1-(4-chloro-
2-fluoro-5-hydroxyphenyl)-3-methyl-4-difluoromethyl-
~2-1,2,4-triazolin-5-one, 0.31 g (0.0026 mole) of
allyl bromide, and 0.35 g (Q.0026 mole) of potassium
15 carbonate in 60 mL of acetone. The yield of 1-(4-
chloro-2-fluoro-5-allyloxyphenyl)-3-methyl-4-difluoro-
methyl-~2 1,2,4-triazolin-5-one was 0.85 g; m.p.
53-55C.
The nmr spectrum was consistent with the proposed
20 structure.
Analysis for C13HllClF3N32
Calc'd: C 46.64, H 3.21, N 12.45;
Found: C 46.79, H 3.32, N 12.59.
Example 7
PREPARATION OF 1-[4-CHLORO-2-FLUORO-5-(1-METHYL-2-
METHOXYETHOXY)PHENYL]-3-METHYL-4-DIFLUOROMETHYL-
~2-1,2,4-TRIAZOLIN-5-ONE
__ _
A stirred mixture of 0.45 g ~0.0015 mole) of
1-~4-chloro-2-fluoro-5-hydroxyphenyl)-3-methyl-4-
30 difluoromethyl-~2-1,2,4-triazolin-5-one and 0.41 g
~0.0017 mole) of sodium hydride in 8 mL of dimethyl-
formamide was war~ed to 90C. The reaction mixture
was cooled to 40C, and 0.37 g (0.0015 mole) of the
tosylate of methoxypropan-2-ol was added in one por-
35 tion. The reaction mixture was heated at temperaturesvarying from 40 to 140C, tben was allowed to cool to
5~
- 14 -
ambient temperature and was stirred for 16 hours. The
reaction mixture was partitioned between water and
methylene chloride. The methylene chloride layer was
washed sequentially with aqueous 10% sodium hydroxide,
5 aqueous 10~ hydrochloric acid, and water. The organic
layer was drled with magnesium sulfate and filtered.
The filtrate was concentrated under reduced pressure
to give 0.38 g of 1-[4-chloro-2-fluoro-5-(1-methyl-
2-methoxyethoxy)phenyl]-3-methyl-4-difluoromethyl-
10 ~ -1, 2,4-triazolin-5-one as an oil.
The nmr spectrum was consistent with the proposed
structure.
Herbicidal Activity
Herbicidal efficacy data are given in Tables 1-5
- 15 below for the present compound of formula l(a)
(Example 2) and the 2-chloro analog of that compound.
The 2-chloro compound is 1-(21~-dichloro-5-propar-
gyloxyphenyl)-3-methyl-4-difluoromethyl-~2-1,2,4-
triazolin-5-one and is disclosed in British Patent No.
20 2,090,250, supra. While the present compound l(a)
differs structurally from the known compound only in
having a fluorine atom instead of chlorine at the C-2
position of the phenyl ring, it was markedly and
unexpectedly more active than the prior compound
25 against a variety of broadleaf plant species in both
preemergence and postemergence applications in
side-by-side tests conducted as described below. Data
for t~e compounds of Examples 3-7 are given in Tables
6 and 7.
The plant species employed in these tests were
selected from the following:
Common Name (Abbrev.) Scientific Name
,
Barnyardgrass (Barngr) Echinochloa crus galli
Field Bindweed (Bindweed) Convovulus arvensis
35 Blue Panicum (Blue Pan) Panicum antidotale
Common Cocklebur (Coclebr) Xanthium pensy~vanicum
Field Corn (Corn) Zea mays
Cotton Gossypium hirsutum
Giant Foxtail (Giantfox) Set ria faberi Herrm.
.Green Foxtail (Greenfox) Setaria viridis
Ivyleaf Morningglory (Ivyglory) Ipomoea hederacea (L.)
or Ipomoea lacumosa
Johnsongrass (Johngr) Sorghum halepense
Rice Oryza sativa
Hemp Sesbania (Sesbania) Sesbania exaltata Raf.
10 Sicklepod (Sicklepd) Cassia obtusifolia L.
Broadleaf Signalgrass (Signalgr) Brachiaria platyphylla
Soybean Glycine max
Velvetleaf (Velvetlf) Abutilon theophrasti
Wheat Triticum aestivl~m
15 Wild Mustard (Wmustard) Brassica kaber
Yellow Nutsedge tYel Nuts) Cyperus esculentus
Yellow Foxtail ~Yellowfox) Setaria lutescens
(Weigel) Hubb.
Seeds or tubers of the plant test species were
planted in furrows in steam sterilized sandy loam soil
contained in disposable fiber flats. The flats had
been filled to a depth of about 6.5 cm with the soil.
A topping soil of equal portions of sand and sandy
loam soil was placed uniformly on top of each flat to
a depth of approximately 0.5 cm.
The flats for the preemergence tests were watered,
then drenched with the appropriate amount of a
solution of the test compound in a mixture of acetone
and water containing a small amount (up to 0.5~ v/v)
of sorbitan monolaurate emulsifier/solubilizer. The
concentration of the test compound in solution was
varied to give a range of application rates, generally
8.0 kg/ha and submultiples thereof. The flats were
placed in a greenhouse and watered regularly at the
soil surface for 21 days at which time phytotoxicity
5~9
- 16 -
data were recorded.
The flats for the postemergence tests were placed
in a greenhouse and watered for 8-10 days, then the
foliage of the emerged test plants was sprayed with a
solution of the test compound in acetone-water
containing up to 0.5% sorbitan ~onolaurate. After
spraying, the foliage was kept dry for 24 hours, then
watered regularly for 21 days, and phytotoxicity data
recorded.
10Herbicidal data are given in Tables 1 and 2 below
for the present compound I(a) and for 1-(2,4-dichloro-
5-propargyloxyphenyl)-3-methyl-4-difluoromethyl-
~-1,2,4-triazolin-5-one (Compound A). In these
tables "V" is vigor, "K" is % kill, and "kg/ha" is
kilograms per hectare. Vi~or ratings vary from 0 to 5
and have the following meaning:
V - 5 = no chemical injury; plants normal
4 = slight injury; plants will or have
already recovered
203 - moderate injury; plants expected to recorer
2 = moderate to severe injury; plants are not
expected to recover
1 = severe injury; plants will not recover
0 = dead plant
25TABLE 1
Compound I(a)~
Preemergence Activity
Rate of Ap lication (k~/ha)
.5000 .2500 -~ .1-2-5 ~ .0625 .0313 .0156
30 Species V K V K V K V K V K V K
BARNGR 0100 0100 0100 0100 0i00 0100
BINDWEED 0 100 0100 0l00 490 480 4 70
BLUE PAN 0 100 0100 0lQ0 0100 0100 0 100
COCKLEBR 0 100 290 290 330 30 5 0
CORN 0100 0100 0100 0100 0100 370
COTTON 380 380 430 4 0 50 40
35 GIANTFOX 0 100 0100 0100 0100 0100 0 100
GREENFOX 0 100 0100 0100 0100 0100 0 100
~2gL~i5~3~
- 17 -
TABLE 1 (Continued)
Compound I(a)*
Pree~er~ence Activity
Rate of Application (kg/ha)
.S000.2500 .1250 .0525 .031-3 .01~6
Species V K V K Y ~ V K V K V K
_. _ _ _ _ _
IVYGLORY O 100 0 lOO O 100 3 90 3 70 3 0JOHNGR O100 0100 0100 0lOO O100 0100
RICE O100 0100 0lOO OlOO 290 340
SESBANIA O lOO O100 390 0lOO 350 4 0
SICKLEPD O lOO OlOO 195 310 40 4 0
SIGNALGR 0 100 0100 0100 0100 0100 3 80
SOYBEAN 0100 0100 0100 0100 390 380
VELVETLF O 100 0100 0100 0100 0100 0 100
WHEAT 0100 0100 0100 280 320 320
WMUSTARD O lOQ O100 0100 0100 450 5 0
YEL NUTS O lOO 260 270 360 310 4 0
YELLOWFOX O 100 0100 0100 0100 0100 3 70
*Compound I(a) is the compound of Example 2, 1-~4-chloro-
2-fluoro-5-propargyloxyphenyl)-3-methyl-4-difluoro-
methyl-~ 2-1, 2,4-triazolin-5-one.
Compound A*
Preemer~gence ~ctivity
Rate of Application ~kg/ha)
.5000 .2500 .l~5b --~b~25 .0313 .01S6
Species V K V K V X V ~ V X V K
_
BARNGR OlOO O100 0lOO O100 0100 0100
BINDWEED O 100 0100 4 0 40 50 5 0
BLUE PAN O 100 0100 0100 0100 0100 0 100
COCKLEBR 3 90 380 480 480 50 5 0
CORN O100 0100 0100 0lOO 270 270
COTTON 350 480 40 5 0 480 40
GIANTFOX O 100 0100 0100 0100 0100 0 100
GREENFOX O 100 0100 0lOO O100 0100 0 100
IVYGLORY O 100 0100 350 40 40 5 0
JOHNGR O100 0100 0100 0100 0100 0100
RICE OlOO O100 0100 19S O100 0100
SESBANIA O 100 0100 390 0lOO 330 4 0
SICKLEPD 2 90 30 4 0 40 40 4 0
SIGNALGR O 100 0100 0100 0100 0100 0 lOO
SOYBEAN O100 0100 290 380 460 40
VELVETLF O lOO O100 0100 0100 0100 0 100
WHEAT O100 0100 0100 370 350 4O
WMUSTARD O lOO O100 4 0 50 50 5 0
YEL NUTS 0 100 280 Z60 340 30 4 0
YELLOWFOX 0 100 0100 0100 0100 0100 3 95
5~
- 18 -
*Compound A is 1-(2,4-dichloro-5-propargyloxyphenyl)-
3-methyl-4-difluoromethyl-~2-1,2,4-triazolin-5-one.
TABLE 2
Compound I(a)*
Postemergence Activity
Rate of Applications (kg/ha)
.5000 .2500 .1250 .06Z5 .0313 .01-56
Species _ K V K V K V K V K V K_ _ _ _ _ _ _ _ _ _
BARNGR O100 0100 0lOn O100 0100 380
BINDWEED O 100 0100 0100 nloo oloo 3 ~0
BLUE PAN O 100 0100 0100 0100 0100 2 90
COCKLEBR O 100 290 390 40 50 5 0
CORN O100 0100 0100 160 230 260
COTTON O100 0100 0100 390 0100 190
GIANTFOX O 100 0100 0100 0100 0100 0 100
GREENFOX O 100 0100 0100 0100 0100 2 90
IVYGLORY O 100 0100 0100 0100 0100 2 80
JOHNGR O100 0100 0100 0100 430 360
RTCE O100 0100 nloo oloo 190 370
SESBANIA O 100 0100 0100 0100 0100 2 90
SICKLEPD O 100 0100 190 0100 330 3 40
SIGNALGR O 100 O100 0100 0100 0100 2 90
SOYBBAN 190 0100 190 270 360 330
VELVETLF O 100 0100 0100 0100 0100 0 100
WHEAT O100 0100 0100 270 430 50
WMUSTARD O 100 0100 0100 0100 370 5 0
YEL NUTS 2 80 0100 260 220 30 5 0
YELLOWFOX O 100 0 100 0 100 0 100 0 100 0 100
*Compound I(a) is the c~mpound of Example 2, 1-(4-chloro-
2-fluoro-S-propargyloxyphenyl)-3-methyl-4-clifluoro-
methyl-~2-1,2,4-triazolin-5-one.
TABLE 2 (Continued)
Compound A*
Postemergence Activity
Rate of Application (kg/ha)
.5000 .2-500 `.1250 .0625 .0313 .0156
S~ V K V K V K V K V K V K
BARNGR O100 0100 0100 380 3 70 0100
BINDWEED O 100 0100 0100 4 60 4 0 0 100
BLUE PAN O 100 0100 0100 0 100. 0 100 0 100
COCKLEBR 2 03 04 0 3 0 5 05 0
CORN O100 0100 0100 290 4 0 460
COTTON O100 0100 0100 0 100 0100 330
- 19 -
TABLE 2 ~Continued)
Compound A~
Postemergence Activity
Rate of Applications (kg/ha)
.5000.2500 .1250 ~ .0~ .0156
Species V K V ~ V ~ V K V K V K
GIANTFOX ~1~0 ~ 1~0 ~1~0 ~1~0 ~1~0 ~1~0
GREENFOX 0100 0 100 0100 0100 O100 0100
IVYGLORY 0100 0 100 0l00 190 190 490
JOHNGR 0100 0 100 0100 0l00 430 190
RICE 0100 0 100 0100 0100 l90 2g0
SESBANIA 0100 0 100 0100 0100 0100 290
SICKLEPn 0100 0 100 0100 5 0 480 50
SIGNAL~R 0100 0 100 0100 0100 0100 0100
SOYBEAN 290 2 80 340 330 4 0 40
VELVETLE 0l00 0 100 0100 0100 290 0100
WHEAT 0100 3 80 270 410 420 50
WMUSTARD 0100 3 20 5 0 5 0 5 0 50
YEL NUTS 290 2 60 3 0 330 4 0 40
YELLOWFOX 0 100 0100 0100 0100 0100 4 70
*Compound A is l-t2,4-dichloro-5-propargyloxyphenyl)-3-
methyl-4-diflu.oromethyl-~2-1,2,4-triazolin-5-one.
In order to better compare herbicidal activity for
the two test compounds, biological efficacy tBE)
figures were calculated from percent kill and vigor
using the equation
BE = % kill ~ X(100 - % kill)
wherein X is a number assigned to the vigor rating
according to the following schedule:
vigor X
0
2 0.75
3 0.25
4 0.12
0
Tables 3 and 4 below show BE values calculated
from the data in Tables 1 and 2 above for the present
compound I(a) and the 2-chloro analog. BE values
s~9
- 20 -
increase with herbicidal efficacy to a maxmimum value
of 100.
TABLE 3
Compound I(a)*
Preemergence Biological Efficacy (BE)
Rate of Application (kg/ha)
.5~00 .250~ .lZ50-.06~5.0313 .0156
Species _ BE BE BE BE BE_ _ _
BARNGR100 100 100 100 100 100
BINDWEED100 100 100 91 82 74
BLUE PAN100 100 100 100 100 100
COCKLEBR100 98 98 48 25 0
CORN 100 100 100 100 100 78
COTTON 85 85 38 12 0 12
GIANTFOX100 100 100 100 100 100
GREENFOX100 100 100 100 100 100
IVYGLORY100 100 100 93 78 25
JOHNGR100 100 100 100 100 100
RICE 100 100 100 100 98 55
SESBANIA100 100 93 100 63 12
SICKLEPD100 100 100 33 12 12
SIGNALGR100 100 100 100 100 85
SOYBEAN100 lOO lOO 100 93 85
VELVETLF100 100 100 100 100 100
WHEAT 100 100 100 95 40 40
WMUSTARD100 100 100 100 56 0
YEL NUTS100 90 93 70 33 12
YELLOWFOX 100 100 100 100 100 78
*Compound I(a) is the compound of Example 2, 1-(4-chloro-
2-fluoro-5-propargyloxyphenyl)-3-methyl-4-difluoromethyl-
-1,2,4-triazolin-5-one.
Compound A*
Preemergence Biological Efficacy (BE)
Rate of Application (kg/ha)
.
.5000 .2500 .1250.0625.0313 .0156
SpeciesBE BE BE BE BE BE
BARNGR100 100 100 100 100 100
BINDWEED100 100 12 12 0 0
BLUE PAN100 100 100 100 100 100
COCKLEBR93 85 82 82 0 0
CORN 100 100 100 100 93 93
COTTON 63 82 12 0 82 12
GIANTFOX100 100 100 100 100 100
- ~L2~5~39
- 21 -
TABLE 3 (Continued)
Compound A*
Preemergc~ 7T~7~fficacy (BE~
Rate of Application (kg/ha)
.5000.2500.1250.06Z5.0313.-0IS-6
BE BE BE BE BE BE
GREENFOX 100 100 100 100 100 100
IVYGLORY 100 100 63 12 12 0
JOHNGR 100100 100 100 100 100
RICE 100100 100 100 100 100
SESBANIA 100 100 93 100 48 12
SIC~LEPD 98 25 12 12 12 12
SIGNALGR 100 100 100 100 100 100
SOYBEAN 100100 98 85 65 12
VELVETLF 100 100 100 100 100 100
WHEAT 100100 100 78 63 12
WMUSTARD 100 100 12 0 0 0
YEL NUTS 100 95 90 55 25 12
YELLOWFOX 100 100 100 100 100 96
*Compound A is 1-(2,4-dichl~ro-5-propargyloxyphenyl)-
3-methyl-4-difluoromethyl-~ -1,2,4-triazolin-5-on~.
- TABLE 4
Compound I(a)~
Postemergence Biological Efficacr
Rate of Application (kg/ha)
.5000.ZSOO.1~5~.U6~5.~313-.0156
Species BE BE BE BE BE BE
__ _ _ _
BARNGR 100100100 . 100 100 85
BINDWEED 100 100 100 100 100 93
BLUE PAN 100 100 100 100 100 98
COCKLEBR 100 98 93 12 0 0
CORN 100100 100 100 83 90
COTTON 100100 100 93 100 100
GIANTFOX 100 100 100 100 100 100
GREENFOX 100 100 100 100 100 98
IVYGLORY 100 100 100 100 100 95
JOHNGR 100100 100 100 38 70
RICE 100100 100 100 100 78
SESBANIA 100 100 100 100 100 98
SICKLEPD 100 100 100 100 48 55
SIGNALGR 100 100 100 100 100 98
SOYBEAN 100100 100 93 70 48
VELVETLF 100 100 100 100 100 100
WHEAT 100100 100 93 38 n
~2~5~9
- 22 -
TABLE 4 (Continued)
Compound I(a)*
ostemergence_Biological Efficacy
Rate of Application ~k~/ha)
.5000.250~.1250.0625 .0313 .-0156
Species _ BE BE BE BE BE_ _ _ _
WMUSTAR~100 100 100 100 78 0
YEL NUTS95 100 90 80 25 0
YELLOWFOX 100 100 100 100 100 100
*Compound I(a~ is the co~pound of Example 2, 1-(4-chloro-
2-fluoro-5-propargyloxyphenyl)-3-methyl-4-difluoromethyl-
-1,2,4-triazolin-5-one.
TABLE 4
Compound A*
Postemergence Biolo~ical Efficacy
Rate of ADDlication (hQ/ka)
.5000.--2500.1250.0625 .0313 .0156
Species BE BE BE BE BE BE
BARNGR 100 100 100 85 78 100
BINDWEED100 100 100 65 12 100
BLUE PAN100 100 100 100 100 100
COCKLEBR75 25 lZ 25 0 0
CORN 100 100 100 98 12 65
COTTON 100 100 100 100 100 48
GIANTFOX100 100 100 100 100 100
GREENFOX100 100 100 100 100 100
IVYGLORY100 100 100 100 100 91
JOHNGR 100 100 100 lOD 38 100
RICE 100 100 100 100 100 98
SESBANIA100 100 100 100 100 98
SICKLEPD100 100 100 0 82 0
SIGNALGR100 100 100 100 100 100
SOYBEAN 98 95 55 48 12 12
VELVETLF100 100 100 100 98 .100
WHEAT 100 85 93 21 30 0
WMUSTARD100 40 0 0 0 0
YEL NUTS98 90 25 48 12 12
YELLOWFOX 100 100 100 100 100 74
*Compound A is 1-(2,4-dichloro-5-propargyloxyphenyl)-
3-methyl-4-difluoromethyl-~2-1,2,4-triazolin-5-one.
Table 5 below shows a comparison of the average or
overall biological efficacy for the present. compound
I(a) and the prior art compound against both weed
~;~46S~3~
- 23 -
grasses and weed broadleaves. The BE values for
grasses represent the average of the BE values in
Table 3 (preemergence) or Table q ~postemergence) for
barnyardgrass, blue panicum, giant foxtail, green
5 ~oxtail, johnsongrass, signalgrass, yellow nutsedge,
and yellow foxtail. The BE values for broadleaves
represent the average for bindweed, cocklebur,
ivyglory, sesbania, sicklepod, velvetleaf, and wild
mustard. As can be seen from the table, both
10 compounds performed equally well against the grasses,
but the present compound was substantially more active
against the more difficult to control broadleaves. In
the preemergence tests against broadleaves, 0.5 kg/ha
of the standard compound was needed for a BE of 99,
15 whereas only 0.125 kg/ha of the present compound was
required for the same level of control. Similarly, in
the postemergence tests, 0.5 kg/ha of the standard
gave a BE value oE 96 while the present compound gave
a BE of 99 at one-fourth the application rate, 0.125
20 kg/ha. Thus, in either preemergence or postemergence
applications against the broadleaves, the present
compound was about four times as active as the
2-chloro compound.
TABLE 5
Average Biolo~ical Efficacy
Preemergence
Rate of Application (k~/ha)
0.50 0.25 0.125 0.0625 0.0313 0.0156
30 Cpd- Species BE BE BE BE PE BE
I~a)* Grasses 100 100 100 100 lO0 95
Broadleaves lO0 99 99 81 59 32
A* Grasses 100 ioo loo loo loo 99
Broadleaves 99 87 68 45 25 l8
s~
- 24 -
TABLE 5 (Continued)
Postemergence
Rate of Application (kg/ha)
0.50 0.25 0.125 0.0625 0.0313 0.0156
5 Cpd. Species BE BE BE BE BE BE
l~a)* Grasses lO0 lO0 lO0 100 91 93
Broadleaves 100 99 99 87 75 fi3
A* Grasses lO0 100 100 98 88 96
Broadleaves 96 81 73 56 56 56
*Compound I ( a) is the compound of Example 2, 1-(4-
chloro-2-fluoro-~-propargyloxyphenyl)-3-methyl-4-
difluoromethyl-~-1,2,4-triaæolin-5-one, and
Compound A is the corresponding
1-(2,4-dichloro-5-propargyl- oxyphenyl) compound.
For the compounds of Examples 3-7, phytotoxicity
data were taken as percent control. Percent control
was determined by a method similar to the 0 to 100
rating system disclosed in "~esearch Methods in Weed
Science," 2nd ed., B. Truelove, Ed.; Southern Weed
Science Society; Auburn University, Auburn, Alabama,
1977. The present rating system is as follows:
651~
Z5
Rating Description
Percent of Main Crop Weed
Control Categories Description Description
0 No effect No crop reduction No weed control
or injury
. _ .. . . . _ . _ . _ _ _
Slight discoloration Very poor weed
or stunting control
20 Slight Some discoloration, Poor weed
effect stunting or stand control
Crop injury more Poor to defi-
pronounced but not cient weed
lasting control
Moderate injury, Deficient weed
crop usually control
recovers
50 Moderate Crop injury more Deficient to
effect lasting, recovery moderate weed
control
Lasting crop Moderate weed
injury no recovery control
Heavy injury and Control somewhat
stand loss less than satis-
factory
Severe Crop nearly des- Satisfactory to
troyed a few good weed
survivors control
Only occasional Very good to
live plants left excellent control
_ _ .
100 Complete Complete crop Complete weed
effect destruction destruction
Herbicidal data at selected application rates are
given for the compounds of Examples 3-7 in Tables 6
and 7 below. The test compounds are identified in the
tables by Example numbers. In the tables "kg/ha" is
kilog-rams per hectare and "% C" is percent control.
~4~S !393
- 26 -
Table 6
~ ~c-e~e~ Ac~
Compound Number* 3 4 S 6 7
Rate (kg/ha) 1.0 0.25 1.0 0.5 0.5
Species % C % C % C
Cotton 50 70 100 20 90
Soybean 100 100 100 90 100
Field Corn 100 100 100 100 100
Rice 100 100 90 100 100
Wheat 100 100 100 100 100
Field Bindweed 100 100 100 100 100
Morningglory 100 100 100 100 100
Velvetleaf 100 100 100 100 100
Barnyar~grass 100 100 100 100 100
Green Foxtail 100 100 100 100 100
Johnsongrass 100 100 100 100 100
Yellow Nutsedge 100 40 100 80 90
*The compound number is the number of the Example in
which the particular compound was prepared.
Table 7
Postemergence Activity
Compound Number* 3 4 5 6 7
Rate (kg/ha) 1.0 0.25 1.0 0.5 0.5
S~ecies ~-~ % C % C ~
Cotton 100 100 100 100 100
Soybean 100 90 100 90 80
Field Corn 70 90 100 30 80
Rice 90 100 100 30 100
Wheat 60 100 100 30 90
Field Bindweed 100 100 100 100 100
Morningglory 100 100 100 100 100
Velvetleaf 100 100 100 100 100
Barnyardgrass 100 100 100 100 100
Green Foxtail 100 100 100 100 100
Johnsongrass 100 90 100 80 90
Yellow Nutsedge 100 50 100 40 90
589
*The compound number is the number of the Example in
which the particular compound was prepared.
For herbicidal application, the active compounds
as ~bove defined are formulated into herbicidal
compositions by admixture in herbicidally effective
a~ounts with adjuvants and carriers normally employed
in the art for facilitating the dispersion of active
ingredients for the particular utility desired,
recognizing the fact that the formulation and mode of
application of a toxicant may affect the activity of
the material in a given application. Thus, for
agricultural use the present herbicidal compounds may
be formulated as granules of relatively large particle
size, water-soluble or water-dispersible granules, as
powdery dusts, as wettable powders, as emulsifiable
concentrates, as solutions or as any of several other
known types o~ formulations, depending on the desired
mode of application.
For preemergence application these herbicidal
compositions are usually applied either as sprays,
dusts, or granules to the areas in which suppression
of vegetation is desired. For postemergence control
of established plant growth, sprays or dusts are most
commonly used. These formulations may contain as
little as 0.5% to as much as 95% or more by weight of
active ingredient.
Dusts are free flowing admixtures of the active
ingredient with finely divided solids such as talc,
natural clays, kieselguhr, flours such as walnut shell
and cottonseed flours, and other organic and inorganic
solids which ac~ as dispersants and carriers ~or the
toxicant; these finely divided solids have an average
particle size of less than about 50 microns. A
typical dust formulation useful herein is one
containing 1.0 part of the herbicidal co~pound and
99.0 parts of talc.
658~3
- 28 -
Wettable powders, also useful formulations for
both pre and postemergence herbicides, are in the form
of finely divided particles which disperse readily in
water or other dispersant. The wettable powder is
5 ultimately applied to the soil either as a dry dust or
as an emulsion in water or other liquid. Typical
carriers for wettable powders inc]ude Fuller's earth,
kaolin clays, silicas, and other highly absorbent,
readily wet inorganic dilutents. Wettable powders
10 normally are prepared to contain about 5-80~ o~ active
ingredient, depending on the absorbency of the
carrier, and usually also contain a small amount of a
wetting, dispersing or emulsifying agent to facilitate
dispersion. For example, a useful wettable powder
15 formulation contains ~0.8 parts of the herbicidal
compound, 17~9 parts of Palmetto clay, and 1.0 part of
sodium lignosulEonate and 0.3 part of sul~onated
aliphatic polyester as ~etting agents. Frequently,
additional wetting agent and/or oil ~ill be added to
20 the tank-mix for post-emergence application to
acilitate dispersion on the foliage and absorption by
the plant.
Other useful formulations for herbicidal applica-
tions are emulsifiable concentrates. ~mulsifiable
25 concentrates are homogeneous liquid or paste composi-
tions dispersible in water or other dispersant, and
may consist entirely of the herbicidal compound and a
liquid or solid emulsifying agent, or may also contain
a liquid carrier, such as xylene, heavy aromatic
30 naphthas, isophorone, or other non-volatile organic
solvent. For h0rbicidal application these
concentrates are dispersed in water or other li~uid
carrier, and normally applied as a spray to the area
to be treated. The percentage by weight of the
35 essential active ingredient may vary according to the
manner in which the composition is to be applied, but
.
6589
- 29 -
.
in general comprises 0.5 to 95% of active ingredient
by weight of the herbicidal composition.
Typical wetting, dispersing or emulsifyin~ agents
used in agricultural formulations include, for
5 example, the alkyl and alkylaryl sulfonates and
sulates and their sodium salts; polyhydric alcohols;
and other types of surface active agents, many of
which are available in commerce. The surface active
agent, when used, normally comprises 1% to 15% by
10 weight of the herbicidal composition.
Other useful formulations for herbicidal
applications include simple solutions of the active
ingredient in a dispersant in which it is completely
soluble at the Aesired concentration, such as acetone,
15 alkylated naphthalenes, xylene or other organic sol-
vents. Granular formulations, wherein the toxicant is
carried on relatively coarse particles, are of
particular utility for aerial distribution or for
penetration of cover crop canopy. Pressurized sprays,
20 typically aerosols wherein the active ingredient is
dispersed in finely divided form as a result of
vaporization of a low boiling dispersant solvent
carrier, such as the Freons, may also be used.
Water-soluble or water-dispersible granules are also
25 useful formulations for herbicidal application of the
present compounds. Such granular formulations are
free-flowing, non-dusty, and readily water-soluble or
water-miscible. These soluble or dispersib~e granular
formulations described in U.S. patent No. 3,920,442,
30 incorporated herein by reference are useful herein
with the present herbicidal compounds.
The active herbicidal compounds of this invention
may be formulated and/or applied with insecticides,
fungicides, nematicides, plant growth regulators,
35 ertilizers, or other agricultural chemicals and may
be used as effective soil sterilants as well as
.~2~6589
- 30 -
selective herbicides in agriculture. In applying an
active compound of this invention, whether formulated
alone or with other agricultural chemicals, an
effective amount and concentration of the active
compound is of course employed.
The active herbicidal compounds of this invention
may be used in combination with other herbicides, e.g.
they may be mixed with, say, an equal or larger amount
of a known herbicide such as chloroacetanilide herbi-
cides such as 2-chloro-N-(2,6-diethylphenyl)-N-
(methoxymethyl)acetamide (alachlor), 2-chloro-N-
(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl)-
acetamide (metolachlor), and N-chloroacetyl-N-(2,6-
diethylphenyl)glycine (diethatyl-ethyl); benzothiadia-
zinone herbicides such as 3-(1-methylethyl)-tlH)-2,1,
3-henzothiadiazin-~-(3H)-one-2,2-dioxide (bentazon);
triazine herbicides such as 6-chloro-N-ethyl-N-(l-
methylethyl)-1,3,5-triazine-2,4-diamine (atrazine),
and 2-[4-chloro-6-(ethylamino)-1,3,5-triazin-2-yl]-
amino-2-methylpropanenitrile (cyanazine); dinitrol-
aniline herbicides such as 2s6-dinitro-N,N-dipropyl-4-
(trifluoromethyl)benzeneamine (trifluralin); and aryl
urea herbicides such as N'-(3,4-di-chlorophenyl)-N,
N-dimethylurea (diuron) anA N,N-dimethyl-N'-[3-(tri-
fluoromethyl)phenyl]urea (fluometuron).
In general, the compounds of this invention havingthe formula
F O
Cl ~ -CN32
in which R is a radical selected from 2-propynyl,
l-methylethyl, 1-methyl-2-propynyl, methoxymethyl,
2-propenyl, and 1-methyl-2-methoxyethyl, may be
~2~5~
- 31 -
prepared by (a) reacting the compound of the formula
Cl~[~-CHF2
N
HO CH3
with R-X, in which R is as defined above and X is a
good leaving group, in the presence of a base, or
alternatively, (b~ reacting a compound of the formula
F O
Cl ~J'~N-H
RO CH3
in which P~ is as defined above, with CHF2-X, in
which X is a good leaving group, in the presence o a
phase transfer catalyst and a base selected from
sodium hydroxide and potassium hydroxide.
The leaving group X is a chlorine, bromine or
iodine atom. When practicing method (a) the base is
an alkali metal carbonate, or alkali metal
bicarbonate, or an alkali metal hydride, and in method
(b) the phase transfer catalyst is a tetralkylammonium
25 halide and the base is sodium hydroxide. In method
(a) the base can be sodium carbonate or potassium
carbonate and in method (b) the phase transfer
catalyst is a tetrabutylammonium halide or a
(triethyl)(benzyl)ammonium halide in which the halide
30 is bromide or chloride.
