CA1245221A - Herbicidal 1-aryl-.delta..sup.2-1,2,4-triazolin-5-ones - Google Patents
Herbicidal 1-aryl-.delta..sup.2-1,2,4-triazolin-5-onesInfo
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- CA1245221A CA1245221A CA000489430A CA489430A CA1245221A CA 1245221 A CA1245221 A CA 1245221A CA 000489430 A CA000489430 A CA 000489430A CA 489430 A CA489430 A CA 489430A CA 1245221 A CA1245221 A CA 1245221A
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- methyl
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
- A01N43/647—Triazoles; Hydrogenated triazoles
- A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
- C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D249/12—Oxygen or sulfur atoms
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- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
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- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
Abstract
Abstract HERBICIDAL 1-ARYL-.DELTA.2-1,2,4-TRIAZOLIN-5-ONES
Novel aryltriazolinone compounds of the formula
Novel aryltriazolinone compounds of the formula
Description
~ ~5~22~
HERBICIDAL l-ARYL-~2-1,2,4-TRIAZOLIN-5-ONES
The invention described in this application pertains to weed control in agriculture, horticul-ture, or other fields where there is a desire to control unwanted plant growth. More specifically, the present application describes novel herbicidal l-aryl-~2-1,2,4-triazolin-5-ones, herbicidal com-positions containing the new compounds, methods for preparing the compounds, and methods for preventing or destroying undesired plant growth by preemer-gence or postemergence application of the herbici-dal 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.
Various herbicidal l-aryl~2-1,2,4-tria-zolin-5-ones are known in the art~ U.S. Patent No.
4,318,731 and corresponding British Patent No.
HERBICIDAL l-ARYL-~2-1,2,4-TRIAZOLIN-5-ONES
The invention described in this application pertains to weed control in agriculture, horticul-ture, or other fields where there is a desire to control unwanted plant growth. More specifically, the present application describes novel herbicidal l-aryl-~2-1,2,4-triazolin-5-ones, herbicidal com-positions containing the new compounds, methods for preparing the compounds, and methods for preventing or destroying undesired plant growth by preemer-gence or postemergence application of the herbici-dal 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.
Various herbicidal l-aryl~2-1,2,4-tria-zolin-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 R2 C
X
wherein Rl is alkyl, R2 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 ' '~r :9~
~Z~S%2~
above genus compounds wherein R2 is alkynyl, halomethyl, or haloethyl, and X is alkoxy, alkenyl-oxy, alkynyloxy, alkoxyalkoxy, hydroxy, halomethyl-oxy, or haloethyloxy.
uropean Patent Application Publication No.
55,105 discloses a series of herbicidal aryltria-zolinones of the formula F O
wherein R is alkyl, alkenyl, or cycloalkyl, X is chlorine or bromine, and Y is hydrogen or alkoxy.
Japanese Kokai 81-32,468 discloses herbicidal aryltriazolinones of the formula Cl o l~N~
wherein R is hydrogen, alkyl, or 2-propenyl, and Rl is methyl or alkoxy.
South African Patent Application No. 78/3182 discloses herbicidal aryltriazolinones of the formula Rn~ - R
2~
X
wherein Rl is alkyl, R2 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 ' '~r :9~
~Z~S%2~
above genus compounds wherein R2 is alkynyl, halomethyl, or haloethyl, and X is alkoxy, alkenyl-oxy, alkynyloxy, alkoxyalkoxy, hydroxy, halomethyl-oxy, or haloethyloxy.
uropean Patent Application Publication No.
55,105 discloses a series of herbicidal aryltria-zolinones of the formula F O
wherein R is alkyl, alkenyl, or cycloalkyl, X is chlorine or bromine, and Y is hydrogen or alkoxy.
Japanese Kokai 81-32,468 discloses herbicidal aryltriazolinones of the formula Cl o l~N~
wherein R is hydrogen, alkyl, or 2-propenyl, and Rl is methyl or alkoxy.
South African Patent Application No. 78/3182 discloses herbicidal aryltriazolinones of the formula Rn~ - R
2~
- 3 -wherein Rn is hydrogen or represents 1 to 4 same or different radicals selected from halogen, nitro, cyano, optionally halo-substituted alkyl, alkoxy, or alkylthio, and optionally substituted phenyl or phenoxy, and Rl is alkyl, alkoxyalkyl, dialkoxy-ethyl, dialkylaminoethyl, or cycloalkyl.
U.S. Patent No~ 4,315,767 discloses herbicidal bicyclic compounds of the following formula Y Q
,~( C112 ~ 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 sulfur, and Z is oxygen, S~O)p, or NR 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 hydro-gen, and when Z is S(O)p then n is 1 to ~.
Additional herbicidal bicyclic compounds based on the aryltriazolinone nucleus are disclosed in U.S. Patent No. 4,Z13,773 and have the following structural formula Y Q
N ~
=4CH2 ) n V (CH3)m ~z~z~
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)-aminocarbonyl, acyl, alkoxycarbonyl, or -CHR7R8 ~herein R7 is hydrogen or alkyl and R8 is cyano, acetyl, hydroxycarbonyl, alkoxycarbonyl, hydroxymethyl, alkoxymethyl, alkylcarbonyloxy-methyl, hydroxycarbonylethenyl, alkoxycarbonyl-ethenyl, or a group -C0-NRllR12 wherein Rll is hydrogen, alkyl, alkenyl, or alkoxy, and R12 is hydrogen or alkyl; X is halogen, cyano, me~hyl, 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, with certain pro-vi sos .
A class of ~2-1,2,4-triazolin-S-ones is dis-closed as fungicides in U.S. 4,098,896. The dis-closed genus has the formula Rl--S--~
. N SR2 wherein R is alkyl, alkenyl, alkynyl, cycloalkyl,or op~ionally substituted phenyl or arylalkyl, Rl is haloalkyl or haloalkenyl, and R2 is optionally substituted alkyl, alkenyl, or alkynyl, or option-ally substituted aryl, arylalkyl, or alkylaryl.
~52~
The compounds of this invention are 1-[4-bromo-2-fluoro-5-(substituted)oxyphenyl]-3-methyl-
U.S. Patent No~ 4,315,767 discloses herbicidal bicyclic compounds of the following formula Y Q
,~( C112 ~ 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 sulfur, and Z is oxygen, S~O)p, or NR 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 hydro-gen, and when Z is S(O)p then n is 1 to ~.
Additional herbicidal bicyclic compounds based on the aryltriazolinone nucleus are disclosed in U.S. Patent No. 4,Z13,773 and have the following structural formula Y Q
N ~
=4CH2 ) n V (CH3)m ~z~z~
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)-aminocarbonyl, acyl, alkoxycarbonyl, or -CHR7R8 ~herein R7 is hydrogen or alkyl and R8 is cyano, acetyl, hydroxycarbonyl, alkoxycarbonyl, hydroxymethyl, alkoxymethyl, alkylcarbonyloxy-methyl, hydroxycarbonylethenyl, alkoxycarbonyl-ethenyl, or a group -C0-NRllR12 wherein Rll is hydrogen, alkyl, alkenyl, or alkoxy, and R12 is hydrogen or alkyl; X is halogen, cyano, me~hyl, 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, with certain pro-vi sos .
A class of ~2-1,2,4-triazolin-S-ones is dis-closed as fungicides in U.S. 4,098,896. The dis-closed genus has the formula Rl--S--~
. N SR2 wherein R is alkyl, alkenyl, alkynyl, cycloalkyl,or op~ionally substituted phenyl or arylalkyl, Rl is haloalkyl or haloalkenyl, and R2 is optionally substituted alkyl, alkenyl, or alkynyl, or option-ally substituted aryl, arylalkyl, or alkylaryl.
~52~
The compounds of this invention are 1-[4-bromo-2-fluoro-5-(substituted)oxyphenyl]-3-methyl-
4-difluoromethyl- -1,2,4-triazolin-5-ones of the formula - F
~r ~ ~ I - CHF2 wherein R is alkyl, alkenyl, alkynyl, alkoxyalkyl 9 or alkyl-S(O)n-alkyl wherein n is 0 to 2.
The present compounds are named in accordance with the numbering system shown in formula I, for the ring atoms of the heterocycle which is the same as the numbering system used in U.S. 4,318,731, supra, for similar compounds.
A subgenus of this invention comprises the compounds of formula I in which R is selected from -CH3~ -C2H5~ -CH~CH3)2~ -CH20CH3~ CH2CH2 3 -CH(CH3)CH20CH3, -CH2CH=CH2, -CH2C-CH, -CHtCH3)C--CH-The presence of a bromine atom at the C-4 position of the phenyl ring in formula I was found to generally give superior cotton selectivity in preemergence applications at application rates at which a variety of weeds are controlled. A
preferred aspect of the invention comprises the compounds in which R is selected from -CH3, -C2H5, -CH(CH3)2, -CH2ocH3~ CH2CH2 3~
-CH2C_CH, and -CH(CH3)C-CH. In a preferred specific embodiment, R is selected from~-CH3, -CH20CH3, and -CH2C-CH.
The present compounds~ which have a fluorine atom at the C-2 position of the phenyl ring, in 2;~
general have herbicidal properties far superior to those of the corresponding compounds having a chlo rine atom at C-2 of the phenyl ring, and are highly active at low application rates against a ~ariety of grassy and broadleaf weed species in both pre-emergence and postemergence applications.
The compounds of this invention may be pre-pared by methods analogous to the methods described in the references above for similar compounds or by methods within the skill of the art.
The compound of formula I in which R is hydro-gen is an important intermediate to the herbicidal compounds of formula I in which R is as defined above, as illustrated in Examples 2-7 below. Other compounds useful as intermediates are the compounds corresponding to formula I in which the -CHF2 sub-stituent is replaced with a hydrogen atom, as il-lustrated in Example lH below.
Preparation of the present compounds is illus-trated in the following examples. All temperatures shown are in degrees Celcius, and reduced pressures for concentration of liquid were produced by a vac-uum pump.
_XAMPLE 1 PREPARATION OF 1-(4-BROMO-2-FLUORO-5~
METHOXYPHENYL)-3-METHYL-4-DIFLUOROMETHYL-~2-1,2,4-TRIAZOLIN-5-ONE
Step A 2-Bromo-4-fluorophenyl methyl carbonate A stirred solution of 561 g (5.0 moles) of 4-fluorophenol in 600 mL of dioxane was cooled in an ice-water bath and 831 g (5.2 moles) of bromine was added dropwise. The complete addition required :,' `
~S22~
1.5 hours, during ~hich the reaction mixture tem-perature was maintained at 14-25C. Following the addition, the ice-water bath was removed, and the reaction mixture temperature rose to 35C. The reaction mixture was stirred for two hours, then 600 mL of water, followed by 520 mL of 10.8N
aqueous sodium hydroxide were added dropwise over 30 minutes and 1 hour respectively. Upon complete addition, the reaction mixture was cooled to 0-lO~C, and 591 g (6.15 moles) of methyl chlorofor-mate was added dropwise over four hours Upon complete addition, the reaction mixture was allowed to warm to ambient temperature and was stirred for 17 hours. After this time, 450 g of aqueous 50~
sodium hydroxide was added to neutralize the reac-tion mixture. The resultant solid was collected by filtration, and the filter cake washed with two 500 mL portions of water. The solid was dried under reduced pressure to give 1211 g of 2-bromo-4-fluorophenyl methyl carbonate; m.p. 75-78C.
The nmr spectrum was consistent with the pro-posed structure.
Step B 2-Bromo-4-fluoro-S-nitrophenyl methyl carbonate A rapidly stirred solution of 946 g (3.8 moles) of 2-bromo-4-fluorophenyl methyl carbonate in 1292 mL of sulfuric acid was cooled to S-10C, and 368 g (4.18 moles) of 70% nitric acid was added dropwise over two hours. Upon complete addition, the reaction mixture was allowed to warm to ambient temperature and was stirred for two hours. The reaction mixture was poured into 5000 mL of ice water. Any material remaining in the reaction vessel was washed into the ice-water with 750 mL of ~2~22~
water. The resultant solid was collected by fil-tration and washed with 1000 mL of water. The solid was dried with mild heat under reduced pres-sure to give 1031 g of 2-bromo-4-fluoro 5-nitro-phenyl methyl carbonate.
The nmr spectrum was consistent with the pro-posed structure.
Step C 2-Bromo-4-fluoro-5-nitrophenol A stirred solution of 1031 g (3.5 moles) of 2-bromo-4-fluoro-5-nitrophenyl methyl carbonate in 3000 mL of 2.3N aqueous sodium hydroxide was heated to reflux and stirred for three hours. The hot reaction mixture was filtered through diatomaceous earth. Any material remaining in the reaction vessel was washed onto the filter cake with 1000 mL
of water. The filtrate was cooled to 8-10C, and 560 mL of concentrated hydrochloric acid was added, with stirring, over one hour. The resultant solid was collected by filtration. Any material remain-ing in the reaction vessel was washed onto the ilter cake with 1000 mL of water. The dried filter cake was recrystallized from toluene to give, in two crops, 543 g of 2-bromo-4-fluoro-5-nitrophenol, m.p. 124-126C.
The nmr spectra were consistent with the pro-posed structure.
Step D 4-Bromo-2-fluoro-5-methoxynitrobenzene A stirred solution of 30.0 g (0.127 mole) of 2-bromo-4-fluoro-5-nitrophenol, 26.9 g (0.19 mole) of methyl iodide, and 26.3 g ~0.19 mole) of potas-sium carbonate in 200 mL of acetone was heated at reflux for five hours. The reaction mixture was ~Z~2;~
g filtered, and the filtrate concentrated under reduced pressure to give a residue The residue was dissolved in methylene chloride and passed through a column of silica gel. The eluate was concentrated under reduced pressure to give 30 g of 4-bromo-2-fluoro-5-methoxynitrobenzene; m.p.
74-76C.
Step E 4-Bromo-~-fluoro-5-methoxyaniline To a stirred solution of 30.0 g (0.12 mole) of 4-bromo-2-fluoro-5-methoxynitrobenzene in 200 mL of acetic acid was added 40 mL of water, followed by the portionwise addition of 30.0 g (0.54 mole) of iron filings during a 2.5 hour period. Upon com-plete addition, the reaction mixture was stirred at 25-35C for one hour. Diethyl ether, 200 mL, was added, and the reaction mixture was filtered through a pad of diatomaceous earth. The filtrate was washed with 200 mL of water, The organic layer was separated and neutralized with solid sodium bicarbonate. The mixture was dried with magnesium sulfate and filtered. The filtrate was concen-trated under reduced pressure to give a residual solid. The solid was recrystallized from petroleum ether to give 23.5 g of 4-bromo-2-fluoro-5-methoxy-aniline; m.p. 60~62C.
Step F Pyruvic acid, 4-bromo-2-fluoro-5-methoxy-phenylhydrazone Under a nitrogen atmosphere, a stirred solu-tion of 23.5 g (0.107 mole) of 4-bromo-2-fluoro-5-methoxyaniline in 150 mL of concentrated hydro-chloric acid was cooled to -9C, and a solution of 7 4 g (0.107 mole) of sodium nitrite in 40 mL of ~Z~2~L
water was added dropwise over two hours. Upon com-plete addi~ion, the reaction mixture was stirred at -9C for 45 minutes, then a solution of 36.0 g (D.160 mole) of stannous chloride in 50 mL of con-centrated hydrochloric acid was added dropwise overone hour. The reaction mixture temperature was maintained at -9 to 0C throughout the addition.
Upon complete addition, the reaction mixture was allowed to warm to ambient temperature and was s-tirred for two hours. After this time, 100 mL of water was added to the reaction mixture, followed by the dropwise addition of a solution of 9.4 g (0.107 mole) of pyruvic acid in 100 mL of water.
Upon complete addition, the reaction mixture was stirred for 30 minutes at ambient temperature. The reaction mixture was filtered to collect a solid.
The solid was dried to give 23.5 g of pyruvic acid, 4-bromo-2-fluoro-5-methoxyphenylhydrazone;
m.p. 156-158C.
Step G 1-(4-Bromo-2-fluoro-5-methoxyphenyl)-3-methyl-~ -1,2,4-triazolin-5-one A stirred solution of 22.7 g (0.074 mole) of pyruvic acid, 4-bromo-2-fluoro-5-methoxyphenyl-hydrazone3 20.5 g (0.074 mole) of diphenylphos-phoryl a~ide, and 7.5 g (0.074 mole) of triethyl-amine in 15D mL of toluene was heated at reflux for four hours. The reaction mixture was cooled and diluted with diethyl ether. The mixture was extracted three times with aqueous 1 molar sodium hydroxide. The combined extracts were washed with diethyl ether and made acidic with concentrated hydrochloric acid. The resultant solid was collected by filtration and washed with water. The solid was dried to gi~e 15.0 g of 1-(4-bromo-2-~Z~2~
fluoro-5-methoxyphenyl)-3-methyl-~2-1,2,4-triazolin-5-one.
The nmr spectrum was consistent with the proposed structure.
Step ~ (4-Bromo-2-fluoro-5-methoxyphenyl)-3-methyl-4-difluoromethyl-~2_1,2,4-triazolin-S-one A stirred solution of 15.0 g (0.050 mole) of 1-(4-bromo-2-fluoro-5-methoxyphenyl)-3-methyl-a2-1,2,4-triazolin-5-one, 5.6 g (0.10 mole) of potassium hydroxide, and 1.6 g (0.005 mole) of tetrabutylammonium bromide in 150 mL of tetrahydro-furan was saturated with gaseous chlorodifluoro-methane. The reaction mixture was stirred at ambient temperature for 16 hours An additional 2.9 g (0.052 mole) of potassium hydroxide was added, and the reaction mixture was again saturated with chlorodiEluoromethane. Upon complete satura-tion, the reaction mixture was stirred for two hours, then diluted with diethyl ether. The mix-ture was washed with water, then with aqueous saturated sodium chloride. The organic layer was dried with sodium sulfate, filtered, and the fil-trate concentrated under reduced pressure to give a residue. The residue was subjected to column chromatography on silica gel. Elution was accom-plished with 2:1 methylene chloride:petroleum ether. The appropriate fractions were combined and concentrated under reduced pressure to give 4.2 g of 1-(4-bromo-2-fluoro-5-methoxyphenyl)-3-methyl-4-difluoromethyl-a2-1,2,4-triazolin-5-one;
m.p. 129-130C.
The nmr and the ir spectra were consistent with the proposed structure.
f~ 2~
Analysis calc'd for CllHgBrF3N302:
C37.52, H 2.58, N 11.93;
Found: C37.38, H 2.35, ~ 11.52.
PREPARATION OF 1-(4-B~OMO-2-FLUORO-5-METHOXY-METHOXYPHENYL)-3-M~THYL-4-DIFLUOROMETHYL-~2-1,2,4-TRIAZOLIN-5-O~E
-Step A 1-(4-Bromo-2 fluoro-5-hydroxyphenyl)-3-methyl-4-difluoromethyl-~ -1,2,~-tria-zolin-5-one A stirred solution of 7.3 g (0.025 mole) of boron tribromide in 30 mL of methylene chloride was cooled to -40~C, and a solution of 3.0 g (0.009 mole) of l-t4-bromo-2-fluoro-5-methoxyphenyl)-3-methyl-4-difluoromethyl-~2-1,2,4-triazolin-5-one (Example 1) in 25 mL of methylene chloride was added dropwise. The reaction mixture temperature was maintained at -40C throughout the addition.
Upon complete addition, the reaction mixture was allowed to warm to ambient temperature and was stirred for 16 hours. The reaction mixture was poured into ice-water, and the mixture extracted with diethyl ether. The extract was dried with sodium sulfate, filtered, and the filtrate concen-trated under reduced pressure to give a residue.
The residue was dissolved in diethyl ether, and the solution was passed through a pad of silica gel.
The eluate was concentrated under reduced pressure to give 2.9 g of 1-(4-bromo-2-fluoro-5-hydroxy-phenyl)-3-methyl-4-difluoromethyl-~2-1,2,4-tria-zolin-5-one.
The nmr and the ir spectra were consistent with the proposed structure.
~Z~2~
Step B 1-(4-Bromo-2-fluoro-5-methoxymethoxy-phenyl)-3-methyl-4-difluoromethyl-Q2_ 1,234-triazolin-5-one To a stirred suspension of 0.15 g ~0.003 mole) of sodium hydride (50% in mineral oil) in 10 mL of toluene was slowly added 1.1 g (0.003 mole) of 1-(4-bromo-2-fluoro-5-hydroxyphenyl)-3-methyl-4-di-fluoromethyl-Q2-1,2,4-triazolin-5-one. N,N-di-methylacetamide (1-2 mL) was added and the reaction mixture was stirred at ambient temperature until it became clearO The reaction mixture was cooled to 20C, and 0.8 g (0.006 mole) of methoxymethyl bro-mide was added. Upon complete addition, the reac-tion mixture was stirred at ambient temperature for 16 hours. The reaction mixture was poured onto ice and allowed to stand for one hour. The organic layer was separated and dried with magnesium sul-fate. The mixture was filtered, and the filtrate subjected to column chromatography on silica gel.
Elution was accomplished with 4:1 methylene chlo-ride:heptane. The appropriate fractions were com-bined and concentrated under reduced pressure to give 0.9 g of 1-(4-bromo-2-fluoro-5-methoxymethoxy-phenyl)-3-methyl-4-difluoromethyl-Q2-1,2,4-tria-zolin-5-one as an oil.
The nmr spectrum was consistent with the pro-posed structure.
Analysis calc'd for C12HllBrF3N3O3:
C 37.72, H 2.83, N 10.99;
Found: C 38.32, H 2.86, N 10.91.
PREPARATION OF 1-(4-BROMO-2-FLUORO-5-P~OPARGYLOXYPHENYL)-3-METHYL-4-DIFLUORO-METHYL-Q2-1,2,4-TRIAZOLIN- 5-ONE
A stirred solution of 2. 5 g ( O. 008 mole) of ~$2;~
1~(4-bromo-2-fluoro-5-hydroxyphenyl)-3-methyl-4-di-fluoromethyl-Q -1,2,4- triazolin-5-one (prepared as in Step A, Example 2~, 1.6 g (0.012 mole) of potassium carbonate, and 1.9 g (0.017 mole) of pro-pargyl bromide in 30 mL of acetone was heated atreflux for 16 hours. Tlle reaction mixture was cooled and concentrated under reduced pressure to give a residue. The residue was dissolved in methylene chloride and subjected to column chroma-tography on silica gel. Elution was accomplished using methylene chloride. The appropriate frac-tions were combined and concentrated under reduced pressure-to give 2.3 g of 1 (4-bromo-2-fluoro-5-propargyloxyphenyl)-3-methyl-4-difluoromethyl-Q2_ 1,2,4-triazolin-5-one; m.p. 70-72C.
The nmr spectrum was consistent with the proposed structure.
Analysis calc'd for C13HgBrF3N302:
C 41.51, H 2.41, N 11.17;
Found: C 41.33, H 2.19, N 11.35.
The following compounds were prepared from 1-(4-bromo-2-fluoro-5-hydroxyphenyl)-3-methyl-4-di-fluoromethyl-Q2-1~2~4- triazolin-5-one (Example 2A) by an alkylation procedure analogous to that descri~ed above in either Example 2B or Example 3:
Example 4, 1-(4-BROMO-2-FLUORO-5-ETHOXY-PHENYL)-3-METHYL-4-DIFLUOROMETHYL-Q2_1,2,4-TRIA-ZOLIN-5-ONE, m.p. 106-108C. The ir and nmr spectra were consistent with the proposed structure.
Analysis calc'd for Cl2HllBrF3N302 C 39.36~ H 3.03, N 11.48;
Pound: C 39.65, H 2.82, N 11.22.
Example 5, 1-[4-BROMO-2-FLUORO-5-(1-METHYL-ETHOXY)-PHENYL]-3-METHYL-4-DIFLUOROMETHYL-Q2-1,2,4-TRIAZOLI~-5-ONE, obtained as an oil. The ir and nmr spectra were consistent with the proposed ~;345;;~Z~L
structure.
Analysis calc'd for Cl3Hl3BrF3N3O2 C 41.07, H 3.45, N 11.05;
Found C 41.03, H 3.19, N 10.93.
Example 6, 1-[4-BROMO-2-FLUOR0-5-(1-METHYL-PROPARGYLOXY)PHENYL]-3-METHYL-4-DIFLU0ROMETHYL-~2-1,2,4-TRIAZOLIN-5-ONE, m.p. 80-82C. The ir and nmr spectra were consistent with the proposed structure.
Analysis calc'd for C14HllBrF3N302:
C 43.10, H Z.84, N 10.76;
Found: C 43.32, H 2.83, N 10.54.
Example 7, 1-~4-BROMO-2-FLUORO-5-(2-~ETH-OXYETHOXY)PHÆNYL]-3-METHYL-4-DIFLUOROMETHYL-~2-1,2,4-TRIAZOLIN-5-ONE, m.p. 81-82C. The ir and nmr spectra were consistent with the proposed structure.
Analysis calc'd for C13H13BrF3N3O3:
C 39.41, H 3.31, N 10.61;
Found: C 39.25, H 3.08, N 10.31.
Herbicidal_Activity The plant test species used in demonstrating the herbicidal activity of compounds of this inven-tion include cotton (Gossypium hirsutum var. Stone-ville), soybean (Glycine max var. Williams), field corn (Zea may~ var. Agway 595S), rice (Oryza sativa var. Labelle), wheat (Triticum aestivium var.
Prodax), field bindweed (Convolvulus arvensis), morningglory (Ipomea lacunosa or Ipomea hederacea), velvetleaf (Abutilon theophrasti), barnyardgrass (Echinochloa crus galli), green foxtail (Setaria viridis), johnsongrass (Sorghum halepense), and yellow nutsedge (Cyperus esculentus).
Seeds or tubers of the plant test species were planted in furrows in steam sterilized sandy loam soil contained in disposable fiber flats. The ~z~z~
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 ~lat 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 o application rates, generally 8.0 kg/ha and sub-multiplies thereof. The flats were placed in a greenhouse and watered regularly at the soil surface for 21 days at which time phytotoxicity data were recorded.
The flats for the postemergence tests were placed in a greenhouse and watered for 8-10 days, then the foilage of the emerged test plants was sprayed with a solution of the test compound in acetone-water containing up to 0.5% sorbitan mono-laurate. After spraying, the foliage was kept dry for 24 hours, then watered regularly for 21 days, and phytotoxicity data recorded.
Phytotoxicity data were taken as percent control. Percent control was determined by a method similar to the 0 to 100 rating system disclosed in "Research 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:
~2~ZZ~
Rating Description Percent of ~5ain Crop Weed Control Categories Description Description O No effect No crop reduction No weed control or injury Slight discoloration Very poor weed or stunting control Slight Some discoloration, Poor weed effect stunting or stand control ~0 Crop injury more Poor to defi-pronounced but not cient weed lasting control __ ~50derate injury, Deficient weed crop usually control recovers ~oderate 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 2~L
Herbicidal data are given for various compounds of the invention in Tables 1 and 2 below. The test compounds are identified in the tables by Example numbers. In the tables "kg/ha"
is kilograms per hectare and "% C" is percent control.
Preemergence Activity Compound Number~ 1 2 3 4 Rate (kg/ha) 0.~625 0.~6250.~625 0.~625 ~ecies --~F-- -~7~0~~~ %C %C
Cotton 0 0 10 0 Soybean 30 95 80 50 Field Corn 100 100 95 80 Rice 90 95 90 70 Wheat 90 95 95 50 Field Bindweed - 95 I~lorningglory9S 100 90 95 Velvetleaf 100 100 100 100 Barnyardgrass 100 100 100 100 Green Foxtail 90 100 100 100 Johnsongrass 90 95 100 100 Yellow Nutsedge 80 - 80 70 Compound Number* 5 6 7 Rate (kg/ha)0.~625 0.~625 0.~625 SDecies %C %C %C
Cotton 0 10 20 Soybean 10 70 50 Field Corn 80 80 90 Rice 80 95 80 Wheat 80 90 40 Field Bindweed - 90 Morningglory 60 90 95 Velvetleaf 100 100 100 Barnyardgrass 80 100 95 Green Foxtail 90 100 100 Johnsongrass 90 100 90 Yellow Nutsedge 10 - 90 *The compound number is the number of the Example in which the particular compound was prepared.
2~
Postemergence Activity Compound Number* 1 2 3 5 6 Rate (kg/ha)0.~25 0.~625 0.~625 G.~25 0.~25 Species %C ~C ~C %C ~OC
Cotton 70 80 50 80 80 Soybean 90 95 95 ~0 90 Field Corn 90 100 100 80 90 Rice 80 100 90 80 95 Wheat 80 95 50 50 95 Field Bindweed - 100 95 90 100 ~lorningglory100 100 100 80 100 Velvetleaf 100 100 100 100 100 Barnyardgrass90 100 95 80 100 Green Foxtail95 100 100 80 100 Johnsongrass 50 100 80 30 80 Yellow Nutsedge 80 - - - -*The compound number is the number of the Example in which the particular compound was prepared.
For herbicidal application, tlle active com-pounds as above defined are Eormulated into herbi-cidal compositions by admixture in herbicidally effective amounts 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 pre-sent 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 con-centrates, as solutions or as any of several otherknown types of formulations, depending on the desired mode of application.
~522~
For preemergence application these herbicidal compositions are usually applied either as sprays, dusts, or granules to the areas in which suppres-sion 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 act as disper-sants and carriers for the toxicant; these finely divided solids have an average particle size of less than about 50 microns. A typical dust formu-lation usefui herein is one containing 1.0 part of the herbicidal compound and 99.0 parts of talc.
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 disp0rsant. The wettable powder is ultimately applied to the soil either as a dry dust or as an emulsion in water or other liquid. Typical carriers for wettable powders include Fuller's earth, kaolin clays, silicas, and other highly absorbent, readily wet inorganic diluents. Wet~able powders normally are prepared to contain about 5-80% of active ingredient, depending on the absorbency of the carrier, and usually also contain a small amount of a we~ting, dispersing or emulsifying agent to facilitate dis-persion. For example, a useful wettable powder formulation contains 80.8 parts of the herbicidal compound, 17.9 parts of Palmetto clay, and 1.0 part 2~L
of sodium lignosulfonate and 0.3 part of sulfonated aliphatic polyester as wetting agents. Frequently, additional wetting agent and/or oil will be added to the tank-mix for postemergence application to facilitate dispersion on the foliage and absorption by the plant.
Other useful formulations for herbicidal applications are emu~sifiable concentrates. Emul-sifiable concentrates are homogeneous liquid or paste composi~ions dispersible in water or other dispersant, and may consist entirely of the herbi-cidal compound and a liquid or solid emulsifying agent, or may also contain a liquid carrier, such as xylene, heavy aromatic naphthas, isophorone, or other non-volatile organic solvent. For herbicidal application these concentrates are dispersed in water or other liquid carrier, and normally applied as a spray to the area to be treated. The per-centage by weight of the essential active ingre-dient may vary according to the manner in which thecomposition is to be applied, but in general com-prises 0.5 to 95% of active ingredient by weight of the herbicidal composition.
Typical wetting, dispersing or e~ulsifying agents used in agricultural formulations include, for example, the alkyl and alkylaryl sulfonates and sulfates and their sodium salts; polyhydric alco-hols; and other types of surface active agents, many of which are available in commerce. The sur-face active agent, when used, normally comprises 1%to 15% by 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 com-pletely soluble at the desired concentration, such ~2~S2Z~
as acetone, alkylated naphthalenes, xylene or other organic solvents. Granular formulations, wherein the toxicant is carried on relatively coarse parti-cles, are of particular utility for aerial distri-bution or for penetra-tion of cover crop canopy.
Pressurized sprays, 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 useful formulations for herbici-dal application of the present compounds. Such granular formulations are free-flowing, non-dusty, and readily water-soluble or water-miscible. These soluble or dispersible granular formulations des-cribed in U.S. Patent No. 3,920,442, are useful herein with the present herbicidal compounds.
The active herbicidal compounds of this inven--tion may be formulated and/or applied with insecti-cides, fungicides, nematicides, plant growth regu-lators, fertilizers, or o-ther agricultural chemi-cals and may be used as effective soil sterilants as well as selective herbicides in agriculture. In applying an active compound of this invention, whe-ther formulated alone or with other agriculturalchemicals, an effective amount and concentration of the active compound is of course employed.
The active herbicidal compounds of this inven-tion may be used in combination with other herbi-cides, e.g. they may be mixed with, say, an equalor larger amount of a known herbicide such as chloroacetanilide herbicides such as 2-chloro-N-(2,6-diethylphenyl)-N-(methoxymethyl)acetamide (alachlor), 2-chloro-N-(2-ethyl-6-methylphenyl)-~Z~22~
N-(2-methoxy-1-methylethyl)acetamide (metolachlor), and N-chloroacetyl-N-(2,6-diethylphenyl)glycine (diethatyl-ethyl); benzothiadiazinone herbicides such as 3-(1-methylethyl)-(lH)-2,1,3-benzothia-diazin-4-(3H)-one-2,2-dioxide (bentazon); triazine herbicides such as 6-chloro-N-ethyl-N-(l-methyl-ethyl)-1,3,5-triazine-2,4-diamine (atra7ine), and 2-4-chloro-6-(ethylamino)-1,3,5-triazin-2-ylamino-2-methylpropanenitrile (cyanazine); dinitrol-aniline herbicides such as 2,6-dinitro-N,N-di-propyl-4-(trifluoromethyl)benzeneamine (triflura-lin); and aryl urea herbicides such as N'-(3,4-di-chlorophenyl)-N,N-dimethylurea (diuron) and N,N-di-methyl-N'-3-(trifluoromethyl)phenylurea (fluo-meturon).
It is apparent that various modifications may be made in the formulation and application of the novel compounds of this invention, without depart-ing from the inventive concepts herein, as defined in the following claims.
~r ~ ~ I - CHF2 wherein R is alkyl, alkenyl, alkynyl, alkoxyalkyl 9 or alkyl-S(O)n-alkyl wherein n is 0 to 2.
The present compounds are named in accordance with the numbering system shown in formula I, for the ring atoms of the heterocycle which is the same as the numbering system used in U.S. 4,318,731, supra, for similar compounds.
A subgenus of this invention comprises the compounds of formula I in which R is selected from -CH3~ -C2H5~ -CH~CH3)2~ -CH20CH3~ CH2CH2 3 -CH(CH3)CH20CH3, -CH2CH=CH2, -CH2C-CH, -CHtCH3)C--CH-The presence of a bromine atom at the C-4 position of the phenyl ring in formula I was found to generally give superior cotton selectivity in preemergence applications at application rates at which a variety of weeds are controlled. A
preferred aspect of the invention comprises the compounds in which R is selected from -CH3, -C2H5, -CH(CH3)2, -CH2ocH3~ CH2CH2 3~
-CH2C_CH, and -CH(CH3)C-CH. In a preferred specific embodiment, R is selected from~-CH3, -CH20CH3, and -CH2C-CH.
The present compounds~ which have a fluorine atom at the C-2 position of the phenyl ring, in 2;~
general have herbicidal properties far superior to those of the corresponding compounds having a chlo rine atom at C-2 of the phenyl ring, and are highly active at low application rates against a ~ariety of grassy and broadleaf weed species in both pre-emergence and postemergence applications.
The compounds of this invention may be pre-pared by methods analogous to the methods described in the references above for similar compounds or by methods within the skill of the art.
The compound of formula I in which R is hydro-gen is an important intermediate to the herbicidal compounds of formula I in which R is as defined above, as illustrated in Examples 2-7 below. Other compounds useful as intermediates are the compounds corresponding to formula I in which the -CHF2 sub-stituent is replaced with a hydrogen atom, as il-lustrated in Example lH below.
Preparation of the present compounds is illus-trated in the following examples. All temperatures shown are in degrees Celcius, and reduced pressures for concentration of liquid were produced by a vac-uum pump.
_XAMPLE 1 PREPARATION OF 1-(4-BROMO-2-FLUORO-5~
METHOXYPHENYL)-3-METHYL-4-DIFLUOROMETHYL-~2-1,2,4-TRIAZOLIN-5-ONE
Step A 2-Bromo-4-fluorophenyl methyl carbonate A stirred solution of 561 g (5.0 moles) of 4-fluorophenol in 600 mL of dioxane was cooled in an ice-water bath and 831 g (5.2 moles) of bromine was added dropwise. The complete addition required :,' `
~S22~
1.5 hours, during ~hich the reaction mixture tem-perature was maintained at 14-25C. Following the addition, the ice-water bath was removed, and the reaction mixture temperature rose to 35C. The reaction mixture was stirred for two hours, then 600 mL of water, followed by 520 mL of 10.8N
aqueous sodium hydroxide were added dropwise over 30 minutes and 1 hour respectively. Upon complete addition, the reaction mixture was cooled to 0-lO~C, and 591 g (6.15 moles) of methyl chlorofor-mate was added dropwise over four hours Upon complete addition, the reaction mixture was allowed to warm to ambient temperature and was stirred for 17 hours. After this time, 450 g of aqueous 50~
sodium hydroxide was added to neutralize the reac-tion mixture. The resultant solid was collected by filtration, and the filter cake washed with two 500 mL portions of water. The solid was dried under reduced pressure to give 1211 g of 2-bromo-4-fluorophenyl methyl carbonate; m.p. 75-78C.
The nmr spectrum was consistent with the pro-posed structure.
Step B 2-Bromo-4-fluoro-S-nitrophenyl methyl carbonate A rapidly stirred solution of 946 g (3.8 moles) of 2-bromo-4-fluorophenyl methyl carbonate in 1292 mL of sulfuric acid was cooled to S-10C, and 368 g (4.18 moles) of 70% nitric acid was added dropwise over two hours. Upon complete addition, the reaction mixture was allowed to warm to ambient temperature and was stirred for two hours. The reaction mixture was poured into 5000 mL of ice water. Any material remaining in the reaction vessel was washed into the ice-water with 750 mL of ~2~22~
water. The resultant solid was collected by fil-tration and washed with 1000 mL of water. The solid was dried with mild heat under reduced pres-sure to give 1031 g of 2-bromo-4-fluoro 5-nitro-phenyl methyl carbonate.
The nmr spectrum was consistent with the pro-posed structure.
Step C 2-Bromo-4-fluoro-5-nitrophenol A stirred solution of 1031 g (3.5 moles) of 2-bromo-4-fluoro-5-nitrophenyl methyl carbonate in 3000 mL of 2.3N aqueous sodium hydroxide was heated to reflux and stirred for three hours. The hot reaction mixture was filtered through diatomaceous earth. Any material remaining in the reaction vessel was washed onto the filter cake with 1000 mL
of water. The filtrate was cooled to 8-10C, and 560 mL of concentrated hydrochloric acid was added, with stirring, over one hour. The resultant solid was collected by filtration. Any material remain-ing in the reaction vessel was washed onto the ilter cake with 1000 mL of water. The dried filter cake was recrystallized from toluene to give, in two crops, 543 g of 2-bromo-4-fluoro-5-nitrophenol, m.p. 124-126C.
The nmr spectra were consistent with the pro-posed structure.
Step D 4-Bromo-2-fluoro-5-methoxynitrobenzene A stirred solution of 30.0 g (0.127 mole) of 2-bromo-4-fluoro-5-nitrophenol, 26.9 g (0.19 mole) of methyl iodide, and 26.3 g ~0.19 mole) of potas-sium carbonate in 200 mL of acetone was heated at reflux for five hours. The reaction mixture was ~Z~2;~
g filtered, and the filtrate concentrated under reduced pressure to give a residue The residue was dissolved in methylene chloride and passed through a column of silica gel. The eluate was concentrated under reduced pressure to give 30 g of 4-bromo-2-fluoro-5-methoxynitrobenzene; m.p.
74-76C.
Step E 4-Bromo-~-fluoro-5-methoxyaniline To a stirred solution of 30.0 g (0.12 mole) of 4-bromo-2-fluoro-5-methoxynitrobenzene in 200 mL of acetic acid was added 40 mL of water, followed by the portionwise addition of 30.0 g (0.54 mole) of iron filings during a 2.5 hour period. Upon com-plete addition, the reaction mixture was stirred at 25-35C for one hour. Diethyl ether, 200 mL, was added, and the reaction mixture was filtered through a pad of diatomaceous earth. The filtrate was washed with 200 mL of water, The organic layer was separated and neutralized with solid sodium bicarbonate. The mixture was dried with magnesium sulfate and filtered. The filtrate was concen-trated under reduced pressure to give a residual solid. The solid was recrystallized from petroleum ether to give 23.5 g of 4-bromo-2-fluoro-5-methoxy-aniline; m.p. 60~62C.
Step F Pyruvic acid, 4-bromo-2-fluoro-5-methoxy-phenylhydrazone Under a nitrogen atmosphere, a stirred solu-tion of 23.5 g (0.107 mole) of 4-bromo-2-fluoro-5-methoxyaniline in 150 mL of concentrated hydro-chloric acid was cooled to -9C, and a solution of 7 4 g (0.107 mole) of sodium nitrite in 40 mL of ~Z~2~L
water was added dropwise over two hours. Upon com-plete addi~ion, the reaction mixture was stirred at -9C for 45 minutes, then a solution of 36.0 g (D.160 mole) of stannous chloride in 50 mL of con-centrated hydrochloric acid was added dropwise overone hour. The reaction mixture temperature was maintained at -9 to 0C throughout the addition.
Upon complete addition, the reaction mixture was allowed to warm to ambient temperature and was s-tirred for two hours. After this time, 100 mL of water was added to the reaction mixture, followed by the dropwise addition of a solution of 9.4 g (0.107 mole) of pyruvic acid in 100 mL of water.
Upon complete addition, the reaction mixture was stirred for 30 minutes at ambient temperature. The reaction mixture was filtered to collect a solid.
The solid was dried to give 23.5 g of pyruvic acid, 4-bromo-2-fluoro-5-methoxyphenylhydrazone;
m.p. 156-158C.
Step G 1-(4-Bromo-2-fluoro-5-methoxyphenyl)-3-methyl-~ -1,2,4-triazolin-5-one A stirred solution of 22.7 g (0.074 mole) of pyruvic acid, 4-bromo-2-fluoro-5-methoxyphenyl-hydrazone3 20.5 g (0.074 mole) of diphenylphos-phoryl a~ide, and 7.5 g (0.074 mole) of triethyl-amine in 15D mL of toluene was heated at reflux for four hours. The reaction mixture was cooled and diluted with diethyl ether. The mixture was extracted three times with aqueous 1 molar sodium hydroxide. The combined extracts were washed with diethyl ether and made acidic with concentrated hydrochloric acid. The resultant solid was collected by filtration and washed with water. The solid was dried to gi~e 15.0 g of 1-(4-bromo-2-~Z~2~
fluoro-5-methoxyphenyl)-3-methyl-~2-1,2,4-triazolin-5-one.
The nmr spectrum was consistent with the proposed structure.
Step ~ (4-Bromo-2-fluoro-5-methoxyphenyl)-3-methyl-4-difluoromethyl-~2_1,2,4-triazolin-S-one A stirred solution of 15.0 g (0.050 mole) of 1-(4-bromo-2-fluoro-5-methoxyphenyl)-3-methyl-a2-1,2,4-triazolin-5-one, 5.6 g (0.10 mole) of potassium hydroxide, and 1.6 g (0.005 mole) of tetrabutylammonium bromide in 150 mL of tetrahydro-furan was saturated with gaseous chlorodifluoro-methane. The reaction mixture was stirred at ambient temperature for 16 hours An additional 2.9 g (0.052 mole) of potassium hydroxide was added, and the reaction mixture was again saturated with chlorodiEluoromethane. Upon complete satura-tion, the reaction mixture was stirred for two hours, then diluted with diethyl ether. The mix-ture was washed with water, then with aqueous saturated sodium chloride. The organic layer was dried with sodium sulfate, filtered, and the fil-trate concentrated under reduced pressure to give a residue. The residue was subjected to column chromatography on silica gel. Elution was accom-plished with 2:1 methylene chloride:petroleum ether. The appropriate fractions were combined and concentrated under reduced pressure to give 4.2 g of 1-(4-bromo-2-fluoro-5-methoxyphenyl)-3-methyl-4-difluoromethyl-a2-1,2,4-triazolin-5-one;
m.p. 129-130C.
The nmr and the ir spectra were consistent with the proposed structure.
f~ 2~
Analysis calc'd for CllHgBrF3N302:
C37.52, H 2.58, N 11.93;
Found: C37.38, H 2.35, ~ 11.52.
PREPARATION OF 1-(4-B~OMO-2-FLUORO-5-METHOXY-METHOXYPHENYL)-3-M~THYL-4-DIFLUOROMETHYL-~2-1,2,4-TRIAZOLIN-5-O~E
-Step A 1-(4-Bromo-2 fluoro-5-hydroxyphenyl)-3-methyl-4-difluoromethyl-~ -1,2,~-tria-zolin-5-one A stirred solution of 7.3 g (0.025 mole) of boron tribromide in 30 mL of methylene chloride was cooled to -40~C, and a solution of 3.0 g (0.009 mole) of l-t4-bromo-2-fluoro-5-methoxyphenyl)-3-methyl-4-difluoromethyl-~2-1,2,4-triazolin-5-one (Example 1) in 25 mL of methylene chloride was added dropwise. The reaction mixture temperature was maintained at -40C throughout the addition.
Upon complete addition, the reaction mixture was allowed to warm to ambient temperature and was stirred for 16 hours. The reaction mixture was poured into ice-water, and the mixture extracted with diethyl ether. The extract was dried with sodium sulfate, filtered, and the filtrate concen-trated under reduced pressure to give a residue.
The residue was dissolved in diethyl ether, and the solution was passed through a pad of silica gel.
The eluate was concentrated under reduced pressure to give 2.9 g of 1-(4-bromo-2-fluoro-5-hydroxy-phenyl)-3-methyl-4-difluoromethyl-~2-1,2,4-tria-zolin-5-one.
The nmr and the ir spectra were consistent with the proposed structure.
~Z~2~
Step B 1-(4-Bromo-2-fluoro-5-methoxymethoxy-phenyl)-3-methyl-4-difluoromethyl-Q2_ 1,234-triazolin-5-one To a stirred suspension of 0.15 g ~0.003 mole) of sodium hydride (50% in mineral oil) in 10 mL of toluene was slowly added 1.1 g (0.003 mole) of 1-(4-bromo-2-fluoro-5-hydroxyphenyl)-3-methyl-4-di-fluoromethyl-Q2-1,2,4-triazolin-5-one. N,N-di-methylacetamide (1-2 mL) was added and the reaction mixture was stirred at ambient temperature until it became clearO The reaction mixture was cooled to 20C, and 0.8 g (0.006 mole) of methoxymethyl bro-mide was added. Upon complete addition, the reac-tion mixture was stirred at ambient temperature for 16 hours. The reaction mixture was poured onto ice and allowed to stand for one hour. The organic layer was separated and dried with magnesium sul-fate. The mixture was filtered, and the filtrate subjected to column chromatography on silica gel.
Elution was accomplished with 4:1 methylene chlo-ride:heptane. The appropriate fractions were com-bined and concentrated under reduced pressure to give 0.9 g of 1-(4-bromo-2-fluoro-5-methoxymethoxy-phenyl)-3-methyl-4-difluoromethyl-Q2-1,2,4-tria-zolin-5-one as an oil.
The nmr spectrum was consistent with the pro-posed structure.
Analysis calc'd for C12HllBrF3N3O3:
C 37.72, H 2.83, N 10.99;
Found: C 38.32, H 2.86, N 10.91.
PREPARATION OF 1-(4-BROMO-2-FLUORO-5-P~OPARGYLOXYPHENYL)-3-METHYL-4-DIFLUORO-METHYL-Q2-1,2,4-TRIAZOLIN- 5-ONE
A stirred solution of 2. 5 g ( O. 008 mole) of ~$2;~
1~(4-bromo-2-fluoro-5-hydroxyphenyl)-3-methyl-4-di-fluoromethyl-Q -1,2,4- triazolin-5-one (prepared as in Step A, Example 2~, 1.6 g (0.012 mole) of potassium carbonate, and 1.9 g (0.017 mole) of pro-pargyl bromide in 30 mL of acetone was heated atreflux for 16 hours. Tlle reaction mixture was cooled and concentrated under reduced pressure to give a residue. The residue was dissolved in methylene chloride and subjected to column chroma-tography on silica gel. Elution was accomplished using methylene chloride. The appropriate frac-tions were combined and concentrated under reduced pressure-to give 2.3 g of 1 (4-bromo-2-fluoro-5-propargyloxyphenyl)-3-methyl-4-difluoromethyl-Q2_ 1,2,4-triazolin-5-one; m.p. 70-72C.
The nmr spectrum was consistent with the proposed structure.
Analysis calc'd for C13HgBrF3N302:
C 41.51, H 2.41, N 11.17;
Found: C 41.33, H 2.19, N 11.35.
The following compounds were prepared from 1-(4-bromo-2-fluoro-5-hydroxyphenyl)-3-methyl-4-di-fluoromethyl-Q2-1~2~4- triazolin-5-one (Example 2A) by an alkylation procedure analogous to that descri~ed above in either Example 2B or Example 3:
Example 4, 1-(4-BROMO-2-FLUORO-5-ETHOXY-PHENYL)-3-METHYL-4-DIFLUOROMETHYL-Q2_1,2,4-TRIA-ZOLIN-5-ONE, m.p. 106-108C. The ir and nmr spectra were consistent with the proposed structure.
Analysis calc'd for Cl2HllBrF3N302 C 39.36~ H 3.03, N 11.48;
Pound: C 39.65, H 2.82, N 11.22.
Example 5, 1-[4-BROMO-2-FLUORO-5-(1-METHYL-ETHOXY)-PHENYL]-3-METHYL-4-DIFLUOROMETHYL-Q2-1,2,4-TRIAZOLI~-5-ONE, obtained as an oil. The ir and nmr spectra were consistent with the proposed ~;345;;~Z~L
structure.
Analysis calc'd for Cl3Hl3BrF3N3O2 C 41.07, H 3.45, N 11.05;
Found C 41.03, H 3.19, N 10.93.
Example 6, 1-[4-BROMO-2-FLUOR0-5-(1-METHYL-PROPARGYLOXY)PHENYL]-3-METHYL-4-DIFLU0ROMETHYL-~2-1,2,4-TRIAZOLIN-5-ONE, m.p. 80-82C. The ir and nmr spectra were consistent with the proposed structure.
Analysis calc'd for C14HllBrF3N302:
C 43.10, H Z.84, N 10.76;
Found: C 43.32, H 2.83, N 10.54.
Example 7, 1-~4-BROMO-2-FLUORO-5-(2-~ETH-OXYETHOXY)PHÆNYL]-3-METHYL-4-DIFLUOROMETHYL-~2-1,2,4-TRIAZOLIN-5-ONE, m.p. 81-82C. The ir and nmr spectra were consistent with the proposed structure.
Analysis calc'd for C13H13BrF3N3O3:
C 39.41, H 3.31, N 10.61;
Found: C 39.25, H 3.08, N 10.31.
Herbicidal_Activity The plant test species used in demonstrating the herbicidal activity of compounds of this inven-tion include cotton (Gossypium hirsutum var. Stone-ville), soybean (Glycine max var. Williams), field corn (Zea may~ var. Agway 595S), rice (Oryza sativa var. Labelle), wheat (Triticum aestivium var.
Prodax), field bindweed (Convolvulus arvensis), morningglory (Ipomea lacunosa or Ipomea hederacea), velvetleaf (Abutilon theophrasti), barnyardgrass (Echinochloa crus galli), green foxtail (Setaria viridis), johnsongrass (Sorghum halepense), and yellow nutsedge (Cyperus esculentus).
Seeds or tubers of the plant test species were planted in furrows in steam sterilized sandy loam soil contained in disposable fiber flats. The ~z~z~
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 ~lat 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 o application rates, generally 8.0 kg/ha and sub-multiplies thereof. The flats were placed in a greenhouse and watered regularly at the soil surface for 21 days at which time phytotoxicity data were recorded.
The flats for the postemergence tests were placed in a greenhouse and watered for 8-10 days, then the foilage of the emerged test plants was sprayed with a solution of the test compound in acetone-water containing up to 0.5% sorbitan mono-laurate. After spraying, the foliage was kept dry for 24 hours, then watered regularly for 21 days, and phytotoxicity data recorded.
Phytotoxicity data were taken as percent control. Percent control was determined by a method similar to the 0 to 100 rating system disclosed in "Research 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:
~2~ZZ~
Rating Description Percent of ~5ain Crop Weed Control Categories Description Description O No effect No crop reduction No weed control or injury Slight discoloration Very poor weed or stunting control Slight Some discoloration, Poor weed effect stunting or stand control ~0 Crop injury more Poor to defi-pronounced but not cient weed lasting control __ ~50derate injury, Deficient weed crop usually control recovers ~oderate 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 2~L
Herbicidal data are given for various compounds of the invention in Tables 1 and 2 below. The test compounds are identified in the tables by Example numbers. In the tables "kg/ha"
is kilograms per hectare and "% C" is percent control.
Preemergence Activity Compound Number~ 1 2 3 4 Rate (kg/ha) 0.~625 0.~6250.~625 0.~625 ~ecies --~F-- -~7~0~~~ %C %C
Cotton 0 0 10 0 Soybean 30 95 80 50 Field Corn 100 100 95 80 Rice 90 95 90 70 Wheat 90 95 95 50 Field Bindweed - 95 I~lorningglory9S 100 90 95 Velvetleaf 100 100 100 100 Barnyardgrass 100 100 100 100 Green Foxtail 90 100 100 100 Johnsongrass 90 95 100 100 Yellow Nutsedge 80 - 80 70 Compound Number* 5 6 7 Rate (kg/ha)0.~625 0.~625 0.~625 SDecies %C %C %C
Cotton 0 10 20 Soybean 10 70 50 Field Corn 80 80 90 Rice 80 95 80 Wheat 80 90 40 Field Bindweed - 90 Morningglory 60 90 95 Velvetleaf 100 100 100 Barnyardgrass 80 100 95 Green Foxtail 90 100 100 Johnsongrass 90 100 90 Yellow Nutsedge 10 - 90 *The compound number is the number of the Example in which the particular compound was prepared.
2~
Postemergence Activity Compound Number* 1 2 3 5 6 Rate (kg/ha)0.~25 0.~625 0.~625 G.~25 0.~25 Species %C ~C ~C %C ~OC
Cotton 70 80 50 80 80 Soybean 90 95 95 ~0 90 Field Corn 90 100 100 80 90 Rice 80 100 90 80 95 Wheat 80 95 50 50 95 Field Bindweed - 100 95 90 100 ~lorningglory100 100 100 80 100 Velvetleaf 100 100 100 100 100 Barnyardgrass90 100 95 80 100 Green Foxtail95 100 100 80 100 Johnsongrass 50 100 80 30 80 Yellow Nutsedge 80 - - - -*The compound number is the number of the Example in which the particular compound was prepared.
For herbicidal application, tlle active com-pounds as above defined are Eormulated into herbi-cidal compositions by admixture in herbicidally effective amounts 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 pre-sent 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 con-centrates, as solutions or as any of several otherknown types of formulations, depending on the desired mode of application.
~522~
For preemergence application these herbicidal compositions are usually applied either as sprays, dusts, or granules to the areas in which suppres-sion 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 act as disper-sants and carriers for the toxicant; these finely divided solids have an average particle size of less than about 50 microns. A typical dust formu-lation usefui herein is one containing 1.0 part of the herbicidal compound and 99.0 parts of talc.
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 disp0rsant. The wettable powder is ultimately applied to the soil either as a dry dust or as an emulsion in water or other liquid. Typical carriers for wettable powders include Fuller's earth, kaolin clays, silicas, and other highly absorbent, readily wet inorganic diluents. Wet~able powders normally are prepared to contain about 5-80% of active ingredient, depending on the absorbency of the carrier, and usually also contain a small amount of a we~ting, dispersing or emulsifying agent to facilitate dis-persion. For example, a useful wettable powder formulation contains 80.8 parts of the herbicidal compound, 17.9 parts of Palmetto clay, and 1.0 part 2~L
of sodium lignosulfonate and 0.3 part of sulfonated aliphatic polyester as wetting agents. Frequently, additional wetting agent and/or oil will be added to the tank-mix for postemergence application to facilitate dispersion on the foliage and absorption by the plant.
Other useful formulations for herbicidal applications are emu~sifiable concentrates. Emul-sifiable concentrates are homogeneous liquid or paste composi~ions dispersible in water or other dispersant, and may consist entirely of the herbi-cidal compound and a liquid or solid emulsifying agent, or may also contain a liquid carrier, such as xylene, heavy aromatic naphthas, isophorone, or other non-volatile organic solvent. For herbicidal application these concentrates are dispersed in water or other liquid carrier, and normally applied as a spray to the area to be treated. The per-centage by weight of the essential active ingre-dient may vary according to the manner in which thecomposition is to be applied, but in general com-prises 0.5 to 95% of active ingredient by weight of the herbicidal composition.
Typical wetting, dispersing or e~ulsifying agents used in agricultural formulations include, for example, the alkyl and alkylaryl sulfonates and sulfates and their sodium salts; polyhydric alco-hols; and other types of surface active agents, many of which are available in commerce. The sur-face active agent, when used, normally comprises 1%to 15% by 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 com-pletely soluble at the desired concentration, such ~2~S2Z~
as acetone, alkylated naphthalenes, xylene or other organic solvents. Granular formulations, wherein the toxicant is carried on relatively coarse parti-cles, are of particular utility for aerial distri-bution or for penetra-tion of cover crop canopy.
Pressurized sprays, 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 useful formulations for herbici-dal application of the present compounds. Such granular formulations are free-flowing, non-dusty, and readily water-soluble or water-miscible. These soluble or dispersible granular formulations des-cribed in U.S. Patent No. 3,920,442, are useful herein with the present herbicidal compounds.
The active herbicidal compounds of this inven--tion may be formulated and/or applied with insecti-cides, fungicides, nematicides, plant growth regu-lators, fertilizers, or o-ther agricultural chemi-cals and may be used as effective soil sterilants as well as selective herbicides in agriculture. In applying an active compound of this invention, whe-ther formulated alone or with other agriculturalchemicals, an effective amount and concentration of the active compound is of course employed.
The active herbicidal compounds of this inven-tion may be used in combination with other herbi-cides, e.g. they may be mixed with, say, an equalor larger amount of a known herbicide such as chloroacetanilide herbicides such as 2-chloro-N-(2,6-diethylphenyl)-N-(methoxymethyl)acetamide (alachlor), 2-chloro-N-(2-ethyl-6-methylphenyl)-~Z~22~
N-(2-methoxy-1-methylethyl)acetamide (metolachlor), and N-chloroacetyl-N-(2,6-diethylphenyl)glycine (diethatyl-ethyl); benzothiadiazinone herbicides such as 3-(1-methylethyl)-(lH)-2,1,3-benzothia-diazin-4-(3H)-one-2,2-dioxide (bentazon); triazine herbicides such as 6-chloro-N-ethyl-N-(l-methyl-ethyl)-1,3,5-triazine-2,4-diamine (atra7ine), and 2-4-chloro-6-(ethylamino)-1,3,5-triazin-2-ylamino-2-methylpropanenitrile (cyanazine); dinitrol-aniline herbicides such as 2,6-dinitro-N,N-di-propyl-4-(trifluoromethyl)benzeneamine (triflura-lin); and aryl urea herbicides such as N'-(3,4-di-chlorophenyl)-N,N-dimethylurea (diuron) and N,N-di-methyl-N'-3-(trifluoromethyl)phenylurea (fluo-meturon).
It is apparent that various modifications may be made in the formulation and application of the novel compounds of this invention, without depart-ing from the inventive concepts herein, as defined in the following claims.
Claims (13)
1. A compound of the formula in which R is a radical selected from the group consisting of methyl, ethyl, 1-methylethyl, methoxymethyl, 2-methoxyethyl, 1-methyl-2-meth-oxyethyl, 2-propenyl, 2-propynyl, and 1-methyl-2-propynyl.
2. The compound of claim 1 in which R is selected from the group consisting of methyl, ethyl, 1-methylethyl, methoxymethyl, 2-methoxyethyl, 2-pro-pynyl, and 1-methyl-2-propynyl.
3. The compound of claim 2 in which R is selected from the group consisting of methyl, meth-oxymethyl, and 2-propynyl.
4. The compound of claim 2 in which R is methyl.
5. The compound of claim 2 in which R is ethyl.
6. The compound of claim 2 in which R is 1-methylethyl.
7. The compound of claim 2 in which R is methoxymethyl.
8. The compound of claim 2 in which R is 2-methoxyethyl.
9. The compound of claim 2 in which R is 2-propynyl.
10. The compound of claim 2 in which R is 1-methyl-2-propynyl.
11. An herbicidal composition comprising an herbicidally effective amount of a compound of claim 1 in admixture with a suitable carrier.
12. A method for controlling undesired plant growth which comprises applying to the locus where control is desired an herbicidally effective amount of a composition of claim 11.
13. The method of claim 12 in which the com-position is applied preemergently to the locus where control is desired and said locus is planted or to be planted with cotton.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000578357A CA1262734A (en) | 1985-08-08 | 1988-09-23 | 1-aryl-d2-1,2,4-triazolin-5-ones compounds as intermediates |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US763,855 | 1985-08-08 | ||
| US06/763,855 US4818276A (en) | 1984-11-20 | 1985-08-08 | Herbicidal 1-aryl-Δ2 -1,2,4-triazolin-5-ones |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000578357A Division CA1262734A (en) | 1985-08-08 | 1988-09-23 | 1-aryl-d2-1,2,4-triazolin-5-ones compounds as intermediates |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA1245221A true CA1245221A (en) | 1988-11-22 |
| CA1262734C CA1262734C (en) | 1989-11-07 |
Family
ID=25068998
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 489430 Expired CA1262734C (en) | 1985-08-08 | 1985-08-27 | 1-aryl-d2-1,2,4-triazolin-5-ones compounds as intermediates |
Country Status (10)
| Country | Link |
|---|---|
| EP (1) | EP0231176A1 (en) |
| AU (1) | AU4729685A (en) |
| BR (1) | BR8507256A (en) |
| CA (1) | CA1262734C (en) |
| DK (1) | DK390385D0 (en) |
| ES (2) | ES8802035A1 (en) |
| IL (1) | IL76199A0 (en) |
| PL (1) | PL255346A1 (en) |
| TR (1) | TR22222A (en) |
| WO (1) | WO1987000730A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4743291A (en) * | 1984-10-31 | 1988-05-10 | Fmc Corporation | Herbicidal aryl triazolinones |
| US4846875A (en) * | 1987-07-21 | 1989-07-11 | Fmc Corporation | Herbicidal triazolinones |
| UA26918C2 (en) | 1988-08-31 | 1999-12-29 | Фмк Корпорейшн | Triazolinone derivative exhibiting herbicidal activity, herbicidal composition, method for inhibition of weed growth |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4404019A (en) * | 1980-12-24 | 1983-09-13 | Sumitomo Chemical Company, Limited | 3-Chloro-1-phenyl-1,2,4-triazolin-5-ones and their use as herbicides |
| CH651029A5 (en) * | 1980-12-25 | 1985-08-30 | Nihon Nohyaku Co Ltd | TRIAZOLINE DERIVATIVES, METHOD FOR THE PRODUCTION THEREOF AND HERBICIDES CONTAINING IT. |
| US4431822A (en) * | 1981-03-30 | 1984-02-14 | Sumitomo Chemical Company, Limited | Tetrahydrophthalimides, and their production and use |
| EP0075267B1 (en) * | 1981-09-19 | 1986-01-15 | Sumitomo Chemical Company, Limited | 4-(2-fluoro-4-halo-5-substituted phenyl)urazols, and their production and use |
| JPS58157771A (en) * | 1982-03-11 | 1983-09-19 | Nippon Nohyaku Co Ltd | Delta2-1,2-4,-triazolin-5-one derivative, its preparation and its use |
-
1985
- 1985-08-23 EP EP85904377A patent/EP0231176A1/en active Pending
- 1985-08-23 WO PCT/US1985/001627 patent/WO1987000730A1/en unknown
- 1985-08-23 BR BR8507256A patent/BR8507256A/en unknown
- 1985-08-23 AU AU47296/85A patent/AU4729685A/en not_active Abandoned
- 1985-08-27 IL IL76199A patent/IL76199A0/en unknown
- 1985-08-27 CA CA 489430 patent/CA1262734C/en not_active Expired
- 1985-08-28 DK DK390385A patent/DK390385D0/en not_active Application Discontinuation
- 1985-09-06 ES ES546768A patent/ES8802035A1/en not_active Expired
- 1985-09-12 PL PL25534685A patent/PL255346A1/en unknown
- 1985-09-13 TR TR22222A patent/TR22222A/en unknown
-
1986
- 1986-11-24 ES ES557223A patent/ES557223A1/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| ES8802035A1 (en) | 1987-03-01 |
| PL255346A1 (en) | 1987-02-23 |
| ES546768A0 (en) | 1987-03-01 |
| ES557223A1 (en) | 1987-10-01 |
| TR22222A (en) | 1986-10-07 |
| CA1262734C (en) | 1989-11-07 |
| EP0231176A1 (en) | 1987-08-12 |
| DK390385D0 (en) | 1985-08-28 |
| AU4729685A (en) | 1987-03-05 |
| WO1987000730A1 (en) | 1987-02-12 |
| IL76199A0 (en) | 1985-12-31 |
| BR8507256A (en) | 1987-10-27 |
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