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AU614633B2 – 5-fluoromethyl-1,2,4-triazolo(1,5-a)-pyrimidine-2- sulfonamides, process for their preparation and compositions for their use as herbicides
– Google Patents

AU614633B2 – 5-fluoromethyl-1,2,4-triazolo(1,5-a)-pyrimidine-2- sulfonamides, process for their preparation and compositions for their use as herbicides
– Google Patents
5-fluoromethyl-1,2,4-triazolo(1,5-a)-pyrimidine-2- sulfonamides, process for their preparation and compositions for their use as herbicides

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Publication number
AU614633B2

AU614633B2
AU36873/89A
AU3687389A
AU614633B2
AU 614633 B2
AU614633 B2
AU 614633B2
AU 36873/89 A
AU36873/89 A
AU 36873/89A
AU 3687389 A
AU3687389 A
AU 3687389A
AU 614633 B2
AU614633 B2
AU 614633B2
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AU
Australia
Prior art keywords
compound
formula
fluoromethyl
document
alkyl
Prior art date
1988-04-19
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AU3687389A
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Inventor
Chrislyn M. Carson
William A. Kleschick
Norman R. Pearson
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Dow Chemical Co

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Dow Chemical Co
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1988-04-19
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1989-04-13
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1991-09-05

1988-04-19
Priority claimed from US07/183,571
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patent/US4959473A/en

1988-04-19
Priority claimed from US07/183,570
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patent/US4904301A/en

1989-04-13
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1989-11-24
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1991-09-05
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1991-09-05
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2009-04-13
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Classifications

C—CHEMISTRY; METALLURGY

C07—ORGANIC CHEMISTRY

C07D—HETEROCYCLIC COMPOUNDS

C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 – C07D477/00

C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 – C07D477/00 in which the condensed system contains two hetero rings

C07D487/04—Ortho-condensed systems

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

A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system

Description

t i DATE 24/11/89 DATE 21/12/89 APPLN. ID 36873 89 PCT NUMBER PCT/US89/01547 INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT) (51) International Patent Classification 4 (11) International Publication Number: WO 89/10368 C07D 487/04, A01N 43/90 Al (43) International Publication Date: 2 November 1989 (02.11.89) (21) Iinernational Application Number: PCT/US89/01547 (74) Agent: KIMBLE, Karen, The Dow Chemical Company, P.O. Box 1967, Midland, MI 48641-1967 (US).
(22) International Filing Date: 13 April 1989 (13.04.89) (81) Designated States: AU, BR, DK, FI, HU, JP, SU.
Priority data: 183,570 19 April 1988 (19.04.88) US 183,571 19 April 1988 (19.04.88) US Published With international search report.
Before the expiration of the time limit for amending the (71) Applicant: THE DOW CHEMICAL COMPANY [US/ claims and to be republished in the event of the receipt of US]; 2030 Dow Center, Abbott Road, Midland, MI amendments.
48640 (US).
(72) Inventors: PEARSON, Norman, R. 3049 Naranja Drive, Walnut Creek, CA 04598 KLESCHICK, William, A. 640 Fig Tree Lane, Martinez, CA 04553 CAR- SON, Chrislyn, M. 4702 Congress, Midland, MI 48640
(US).
(54) Title: 5-FLUOROMETHYL-1,2,4-TRIAZOLO[1,5-a]-PYRIMIDINE-2-SULFONAMIDES, PROCESS FOR THEIR PREPARATION AND COMPOSITIONS FOR THEIR USE AS HERBICIDES (57) Abstract ,2,4-triazolo[ 1,5-a]pyrimidine-2-sulfonamides are prepared from 2-benzylthio- 5-fluoromethyl-1,2,4-triazolo[l,5-a]-pyrimidines and found to be herbicidal and selective to wheat and cotton, and some compounds are degradable in the soil.
li i i i t g (:1 i
P
i;rr :f 1~ i-I~
I
i t r WO 89/10368 PCT/US89/01 547 -1- 5-FLUOROMETHYL-1,2,4-TRIAZOLO[1,5-a]- PYRIMIDINE-2-SULFONAMIDES, PROCESS FOR THEIR PREPARATION AND COMPOSITIONS FOR THEIR USE AS
HERBICIDES
The present invention concerns a new class of sulfonamides for use as herbicides, including their preparation and compositions.
The usefulness of herbicides for the control of unwanted vegetation in crops is greatly reduced when the herbicide does not dissipate in the environment at a sufficiently rapid rate that it is effectively not present when succeeding crops are planted. This is particularly true when the succeeding crop is highly susceptible to the herbicide. For this reason compounds possessing good herbicidal effectiveness that are, in addition, readily degradable in the soil are especially valuable.
The substituted 1,2,4-triazolo[1,5-a]pyrimidine- 2-sulfonamides disclosed in European Application 0142152A, published May 22, 1985, are known to be herbicidal, to be especially phytotoxic to certain broadleaf weeds, and to possess selectivity toward crops, such as wheat, rice, corn, soybeans, and cotton.
I
1 ~Il i WO 89/10368 PCT/US89/01547 -2- Many of these compounds are, however, relatively persistent in the soil. As a consequence they often cannot be used where soil degradation is not sufficiently fast to preclude excessive carry-over from one crop to another, especially where the succeeding crop is a relatively susceptible crop to that herbicide.
It has now been found that 1,2,4-triazolo[1,5a]-pyrimidine-2-sulfonamides possessing a fluoromethyl substituent in the 5-position of the pyrimidine ring are markedly more degradable in the soil than are related compounds possessing other substituents, and, in addition, are outstanding selective herbicides for use in controlling unwanted vegetation in many crops. In particular, fluoromethyl-1,2,4-triazolo1 ,5-a]-pyrimidine-2sulfonamide compounds of the formula
Y’
R
2
R
1 N
N
2 5 NH-SO2 N CHF R3
(I)
wherein: Y’ represents H, CH 3
C
2
H
5
OCH
3
OC
2
H
5 or SCH 3
R
1 represents H, F, Cl, Br, CH 3
CF
3
NO
2 i 3 C0 2 (CI-C4 alkyl), or CON(C 1
-C
4 alkyl) 2 i ii 1 1 ~i I 1 1 ;s y -3- 2 R represents H or CH 3 and R represents F, Cl, Br, NO2, CO2(C -C4 alkyl), CON(CI-C 4 alkyl) 2
OCH
3 or OC 2
H
5 J 5 1 2 1 3 2 with the provisos a) that R and R are not simultaneously
NO
2 CO2(CI-C 4 alkyl), or CON (CI-C alkyl) 2 and b) that when R and R both represent F, Cl, or Br and Y’ is OC2H, R is CH; and agriculturally acceptable salts thereof; are soil degradable herbicides that can be used in situations where Icrops are rotated. They are especially useful for the control of unwanted vegetation in cotton and wheat and can be used in many other crops.
C*
S 0
C
*The 5-fluoromethyl-l,2,4-triazolo[l,5-a]- pyrimidine moiety containing intermediates utilized in the preparation of the compounds of Formula which are depicted by the formula 2 y 2 0
Y
N-N
T CH 2
F
N
wherein: eo I
(II)
SY represents H, Cl, OH, CH 3
C
2
H
5
OC
2
H
5 or OCH and :1i WO 89/10368 rcr/US89/01 547 represents HS, (C-C4s alkyl)thio, benzylthio, or ClSO 2 are an integral part of the invention as are intermediates of Formula wherein Y’ represents OH or Cl.
The biodegradable herbicides are those of Formula in which Y’ represents hydrogen, methyl, ethyl, methoxy, ethoxy, or methylthio and R 1, R 2 and 3 are as defined before. Specific examples include 5-fluoromethyl-N-(2,6-dichlorophenyl-1 ,2,4-triazolo- [1 ,5-alpyrimidine-2-sulfonamide, 5-fluoromethyl-7methyl-N-(2,6-dichloro-3-methylphenyl)-12,4triazoloil,5-a]-pyrimidine-2-sulfonamide, f luoromethyl-7-methoxy-N-(2,6-dif luoro-3methylphenyl)-l,2,4-triazolo[l -2-sulfonamide, 5-fluoromethyl-7-methylthio-N-(2- -me thoxy-6 tr if luorome thyl) phenyl)-1 ,2,4 LI 20 triazolofi ,5-a]-pyrimidine-2-sulfonamide, f luoromethyl-7-ethoxy-N-( 2, 5-dichloro-3methylphenyl)-l,2,4-triazolo[l ,5-a]-pyrimidine-2sulfonamide, 5-fluoromethyJ.-7-ethoxy-N-(2,6-difluoro- 3-methylphenyl)-1 ,2,4-triazolol ,5-alpyrimidine-2-., sulfonamide, and 5-fluoromethyl-7-ethoxy-N-(2methoxy-6-(trifluoromethyl)phenyl)-I ,2,4-triazolo[l alpyrimidine-2-sulf onamide. Compounds in which Y’ represents hydrogen, methoxy, ethoxy or methylthio are preferred as are compounds in which R 1 represents chioro, fluoro, bromo, or trifluoromethyl and R 3 represents chloro! fluoro, bromo, or methoxy. Also preferred are compounds whe re Y’ is ethoxy, and R and R 3 both represent F, Cl, or Br, and R 2 represents WO 89/10368 PCT/US89/0o547
CH
3 Compounds in which R 2 represents methyl are additionally preferred.
The term “agriculturally acceptable salts” is employed herein to denote compounds wherein the acidic sulfonamide proton of the compound of Formula is replaced by a cation which is not herbicidal, especially to crop plants, nor significantly deleterious to the applicator, the environment, or the ultimate user of any crop being treated.
Suitable cations include, for example, those derived from alkali or alkaline earth metals and those derived from ammonia and amines. Preferred cations include sodium, potassium, magnesium, and cations of the formula R5R6R7NH wherein R 5
R
6 and R 7 each, independently represents hydrogen or C 1
-C
12 alkyl, C3-C 12 cycloalkyl, or C 3
-C
12 alkenyl, each of which is optionally substituted by one or more hydroxy, CI-C 8 alkoxy, C 1 -Cg alkylthio or phenyl groups.
Additionally, any two of R 5
R
6 and R7 together may represent an aliphatic difunctional moiety containing 1 to 12 carbon atoms and up to two oxygen or sulfur atoms. Salts of the compounds of Formula can be. prepared by treatment of compounds of Formula with a metal hydroxide, such as sodium hydroxide, potassium hydroxide, or magnesium hydroxide, or an amine, such as ammonia, trimethylamine, hydroxyethylamine, bisallylamine, 2butoxyethylamine, morpholine, cyclododecylamine, or benzylamine.
U
I
WO 89/10368 PCT/US89/01547 -6- The terms “alkyl”, “alkenyl”, “alkoxy” and “alkylthio” as used herein includes straight chain and branched chain moieties. Thus, typical alkyl groups are methyl, ethyl, 1-methylethyl, 1,1dimethylethyl, propyl, 2-methylpropyl, 1-methylpropyl, and butyl.
The compounds of Formula can be prepared by the appropriate general methods disclosed in published European Application 0142152A. For example, a 4-fluoroacetoacetate ester can be combined with a 5-mercapto-, 5-alkylthio-, or 5-benzylthio-3amino-1,2,4-triazole in refluxing glacial acetic acid and allowed to react for several hours. The crystals that form on cooling can be collected and dried to obtain a compound of Formula (II) wherein Y represents OH and T represents HS, (C 2
-C
4 alkyl)thio, or benzylthio. Treatment of this intermediate with excess refluxing phosphorus oxychloride for several hours and distilling the excess phosphorus oxychloride from the mixture produces a reaction mixture which can be dissolved in a water immiscible solvent, such as methylene chloride, and then contacted with water. Removal of the solvent leaves a compound of Formula (II) wherein Y represents Cl and T is unchanged. The Y moiety in this intermediate can be converted to methoxy or ethoxy when T represents (C 2
-C
4 alkyl)thio or benzylthio by allowing the intermediate to stand in a solution of methanol or ethanol containing about an equimolar quantity of sodium methoxide or sodium ethoxide.
In a similar manner, intermediates of Formula 3 (II) in which Y represents hydrogen, methyl, or ethyl and T represents mercapto, alkylthio, or benzylthio 1 1 i! -i ,f t| WO 89/10368 PCT/US89/01547 -7can be prepared by condensation or a 1,3-dicarbonyl compound of the formula RC(0)CH 2
C(O)CH
2 F wherein R represents hydrogen, methyl, or ethyl with a mercapto-, 5-alkyl, or 5-benzyl-2-amino-1,2,4triazole in refluxing glacial acetic acid. The two isomers that may form can be separated by conventional means, such as liquid-liquid chromatography or fractional crystallization.
Treatment of intermediates of Formula (II) wherein Y represents Cl, ethoxy or methoxy, and T represents mercapto, C 2
-C
4 alkylthio, or benzylthio with chlorine in mixture of a water immiscible, unreactive solvent, such as chloroform, and water or 1 in aqueous acetic acid at about 0°C leads to 2-chlorosulfonyl-1,2,4-triazolo[1,5-a]pyrimidine intermediates of Formula (II) (T represents chlorosulfonyl and Y represents Cl, ethoxy or methoxy). These intermediates can be recovered by conventional means.
2-Chlorosulfonyl-5-fluoromethyl-1,2,4of Formula (II) can be condensed with appropriately substituted anilines as described in published European Application 0 1 42152A to obtain the biodegradable herbicides of Formula It is often, however, preferred to condense them with an appropriately substituted N-trialkylsilylaniline (typically, trimethyl or triethyl), essentially in this procedure the compound of Formula (II) wherein T represents C1S0 2 and the appropriately substituted N-trialkylsilylaniline are combined in an organic solvent, such as acetonitrile, containing a catalyst, such as dimethyl sulfoxide, and allowed to react at ambient temperature for several hours. The 3 3 i.s i s i WO89/10368 PCT/US89/01547 WO 89/10368 -8reaction mixture is contacted with an aqueous reagent, often after replacing the reaction solvent with a water-immiscible solvent, such as methylene chloride. The desired product can be recovered from the resulting mixture by conventional means, such as by evaporation of the solvents or by addition of a miscible solvent in which the product is not soluble, such as hexane.
Compounds of Formula in which Y’ represents methoxy, ethoxy or methylthio can be prepared from compounds of Formula in which Y’ represents chloro by combining the latter with about two moles of sodium methoxide in methanol, sodium ethoxide in ethanol, or sodium methanethiolate in an alcohol, respectively. The reactions proceed readily at ambient temperature or with cooling. The products can be recovered by adding an acid, such as acetic acid, and water, and, if desired, can be purified by conventional means.
5-alkylthio-, and 3-amino-1,2,4-triazoles and the substituted anilines required for the preparation of the herbicides and intermediates of the present invention are known in the art. The substituted N-trialkylsilylanilines can be prepared by the reaction of the correspondingly substituted anilines with a trialkylsilyl halide, such as trimethylsilyl bromide or triethylsilyl chloride, and a tertiary amine base in an anhydrous, inert organic solvent using the general procedures described in the journal Synthesis, 1981, 368-9. The substituted N-trialkyl-silylanilines obtained can be purified by distillation.
i- WO 89/10368 PCT/US89/01547 -9- The herbicides of Formula degrade surprisingly rapidly in most agricultural soils, a property conferred upon them by the presence of the substituent. Thus, whereas typical substituted 1,2,4-triazolo[l,5-a]pyrimidine-2- -sulfonamide herbicides have half-lives in moist sandy loam soil with moderate amounts of soil organic matter at growing season temperatures of greater than about 30 days and as a result can remain in the soil in deleterious amounts from one crop planting until the next, the selected herbicides of Formula have half-lives of less than 30 days and often less than two weeks under the same conditions. Compounds of Formula wherein Y’ represents hydrogen, methoxy, or methylthio are especially readily degraded in the soil, having half-lives of 6 to 20 days. Such compounds are preferred because the threat of carryover is further reduced -hen compounds having halflives of less than 21 days are employed. Because of their degradation, the 5-fluoromethyl compounds of Formula do not generally remain in the soil in deleterious amounts from one crop planting until the next when applied at typical herbicide rates and, 2 especially at typical selective herbicide rates. The degradation appears to be mainly biological in nature.
The phenomenon of degradation of a herbicide in the soil is influenced by not only the chemical and physical nature of a herbicide, but also the nature of the soil, the climatic conditions, and the previous use of the soil. Accordingly, degradation rates must be viewed as ranges, rather than as specific numbers. A discussion of the phenomenon can a 1 WO 89/10368 PCr/ USSBI/o547 be found in “Herbicides: Physiology, Biochemistry, Ecology”, Volume 2, by L. J. Audus. Most agricultural soils are located in temperate climates, experience considerable rainfall (or are irrigated), are used for agriculture in a continuous way, and have considerable capability to degrade synthetic organic chemicals. Herbicides having half-lives of greater than about a month, however, are known to have varying degrees of carry-over problems in typical agricultural soils found in temperate climates. Herbicides having half-lives of less than one month are generally free of such problems in most circumstances. Typical agricultural soils in temperate climates contain clay and sand or silt, to 30 percent water, and 0.5 to 8 percent organic matter. The average temperature ranges from 21 to 32°C during growing seasons and 0 to 210°C during offseasons.
The 5-fluoromethyl-1,2,4-triazolo(1 pyrimidine-2-sulfonamide herbicides of Formula (I) are useful for the control of unwanted vegetation in valuable crops when applied at selective rates, especially in postemergence applications. The control of unwanted vegetation in wheat and cotton crops is especially important, but selectivity is observed in some instances for barley, soybeans and r other grassy and broadleaf crops. Selectivity is a function of not only the chemical and physical nature of a herbicide, but also the method of application, the variety of the crop plant, the specific weeds present, the climatic conditions of temperature and humidity, the soil type and condition (for preemergence applications), and other factors. The t WO 89/10368 PCT/US89/01547 -11compounds of Formula are selective to wheat and cotton and to other crops under most circumstances, particularly in postemergence applications, but certain circumstances may be contra-indicated for some of the compounds. These will be readily apparent to those skilled in the art using the general precepts of herbicidal action and the teachings herein. Compounds of Formula wherein
R
2 represents methyl are often especially selective.
compounds of Formula are useful as general herbicides at application rates greater than the selective rates.
General herbicide action is usually observed for compounds of Formula at rates of greater than 100 g/Ha for either preemergence or postemergence applications. The selective control of susceptible weeds in cotton can generally be accomplished at application rates of 1 to 60 g/Ha and in wheat at rates of 1 to 150 g/Ha. An appropriate rate for each crop, compound and circumstance can be determined by simple range finding tests using the teachings herein.
The term “herbicide” is used herein to mean an active ingredient which controls or adversely modifies growth of plants. By “growth controlling” or “herbicidally effective” amount is meant an amount of active ingredient which causes an adversely modifying effect and includes deviations from natural development, killing, regulation, dessication, retardation, and the like. The terms “plants” and “weeds” are meant to include germinant seeds, emerging seedlings and established vegetation.
jv M, R represents H, F, C1,
CO
2 (C -C 4 alkyl), or CON(C 1
-C
4 alkyl) 2
R
2 represents H or CH 3 and Br, CH 3
CF
3
NO
2 i /2 WO 89/10368 I. Fc~~-rr PCT/US89/01547 -12- The compounds of Formula can be used directly as herbicides, but it is generally preferable to first prepare a herbicidal composition containing one or more of the compounds of Formula in combination with an agriculturally acceptable adjuvant or carrier. Suitable adjuvants or carriers should not be phytotoxic to valuable crops, particularly at the concentrations employed in applying the compositions for selective weed control in the presence of crops, and should not react chemically with compounds of Formula or other composition ingredients. Such mixtures can be designed for application directly to plants or their locus or can be concentrates or formulations which are normally diluted with additional carriers and adjuvants before application. They can be solids, such as, for example, dusts, granules, water dispersible granules, or wettable powders, or liquids, such as, for example, emulsifiable concentrates, solutions, emulsions or suspensions.
Suitable agricultural adjuvants and carriers that are useful in preparing the herbicidal mixtures of the invention are well known to those skilled in the art.
Liquid carriers that can be employed include water, toluene, xylene, petroleum naphtha, crop oil, acetone, methyl ethyl ketone, cyclohexanone, trichloro-ethylene, perchloroethylene, ethyl acetate, amyl acetate, butyl acetate, propylene glycol monomethyl ether and diethylene glycol monomethyl ether, isopropyl alcohol, amyl alcohol, ethylene glycol, propylene glycol, glycerine, and the like, ii i i r i t WO 89/10368 PCT/US89/01547 -13- Water is generally the carrier of choice for the dilution of concentrates.
Suitable solid carriers include talc, pyrophyllite clay, silica, attapulgus clay, kieselguhr, chalk, diatomaceous earth, lime, calcium carbonate, bentonite clay, Fuller’s earth, cotton seed hulls, wheat flour, soybean flour, pumice, wood flour, walnut shell flour, lignin, and the like.
ii It is frequently desirable to incorporate one or more surface-active agents into the compositions having as its active ingredient a compound of Formula Such surface-active agents are advan-tageously employed in both solid and liquid compositions, especially those designed to be diluted with carrier before application. The surface-active agents can be anionic, cationic or nonionic in character and can be employed as emulsifying agents, wetting agents, suspending agents, or for other purposes. Typical surface active agents include salts of alkyl sulfates, such as diethanolammonium lauryl sulfate; alkylarylsulfonate salts, such as calcium dodecylbenzenesulfonate; alkylphenol-alkylene oxide addition products, such as nonylphenol-C 18 ethoxylate; alcohol-alkylene oxide addition products, such as tridecyl alcohol-C 16 ethoxylate; soaps, such as sodium stearate; alkylnaphthalenesulfonate salts, such as sodium dibutylnaphthalenesulfonate; dialkyl esters of sulfosuccinate salts, such as sodium di(2ethylhexyl) sulfosuccinate; sorbitol esters, such as sorbitol oleate; quaternary amines, such as lauryl trimethylammonium chloride; polyethylene glycol esters of fatty acids, such as polyethylene glycol stearate; block copolymers of ethylene oxide and i 1- I 1ii~ PCT/US89/01 547 WO 89/10368 -14propylene oxide; and salts of mono and dialkyl phosphate esters.
Other adjuvants commonly utilized in agricultural compositions* Include antifoam agents, compatibilizing agents, sequestering agents, neutralizing agents and buffers, corrosion inhibitors, dyes, odorant, penetration aids, spreading agents, sticking agents, dispersing agents, thickening agents, freeze point depressants, antimicrobial agents, and the like. The addition of crop oil and crop oil concentrates is typical. The compositions can also contain other compatible components, for example, other herbicides, plant growth regulants, fungicides, insecticides, and the like and can be formulated with solid, particulate fertilizer carriers such as ammonium nitrate, urea and the like or with liquid fertilizers.
The concentration of the active ingredients in the herbicidal compositions having a compound of Formula as its ictive ingredient is generally from 0.001 to 98 percent by weight. Concentrations from 0.01 to 90 percent by weight are often employed.
In compositions designed to be employed as concentrates, the active ingredient is generally present in a concentration from 5 to 98 weight percent, preferably 10 to 90 weight percent. Such compositions are typically diluted with an inert carrier, such as water, before application. The diluted compositions usually applied to plants or their locus generally contain 0.001 to 5 weight active ingredient and preferably contain 0.01 to 1.0 percent.
2
I
WO89/10368 PCT/US89/01547 The present compositions can be applied by the use of conventional ground or aerial dusters and sprayers, by addition to irrigation water, and by other conventional means known to those skilled in the art.
The following examples are presented to illustrate the invention and should not be interpreted as limiting the scope.
STARTING MATERIALS/INTERMIEDATES Example A. Preparation of t-Butyl 4- Fluoroacetoacetate A solution containing 12.6 g (125 mmol) of diisopropylamine in 90 ml of dry tetrahydrofuran was cooled to -780C and 52.4 ml of 2.5M n-butyllithium (131 mmol) was added. A solution of 14.5 g (125 mmol) of t-butyl acetate in 10 ml of tetrahydrofuran was then added dropwise over a 30 min period with stirring and allowed to react for another 30 min at -78°C. A solution of 6.00 g (56.6 mmol) of ethyl fluoroacetate in tetrahydrofuran was added dropwise with stirring to the resultant pale yellow solution and the mixture allowed to react for another 30 min at -780C and then allowed to stir and warm to ambient temperature over one hour. The resulting pale yellow solution was diluted with 250 ml of ether and the ethereal solution was extracted with 250 ml of 1N HC1, 250 ml of water, and 250 ml of saturated aqueous sodium bicarbonate. The solution was then dried over magnesium sulfate and distilled at atmospheric pressure to remove the solvents. The residue was fractionally distilled under reduced pressure from a q T i j pi: li 3
BIC-P
SWO 89/10368- -16- PCT/US89/01547
~I”
based-washed and oven-dried flask containing a few potassium bicarbonate crystals to obtain 7.00 g percent of theory) of the desired product as a colorless oil boiling at 72-74 C at 10 torr. The proton and fluorine nmr spectra were consistent with the assigned structure.
Example B. Preparation of fluoromethyl-7- -hydroxy-1 ,2,4-triazolo[1 a]pyrimidine A solution containing 20.0 g (114 mmol) of t-butyl 4 -fluoroacetoacetate (prepared in Example A), 23.4 g (114 mmol) of 3-amino-5-benzylthio-1,2,4triazole in 250 ml of glacial acetic acid was heated at reflux with stirring for 5.5 hr and then allowed to cool and stand overnight. The crystals that formed were ground to reduce their size and then recovered by filtration and dried in a vacuum oven to obtain 18.3 g (55 percent of theory) of the title product as a white powder melting with decomposition at 214-218 0
C.
Elemental Analysis: Calc. for CI 3
H
1 1
FN
4 0S: 53.79; 3.82; 19.29 Found: 53.35; 3.98; 19.00 4 1::3 r f I–i, i r WO 89/10368 PCT/US89/01547 -17- Example C. Preparation of fluoromethyl-7-chloro-1,2,4-triazolo[l A mixture of 17.0 g (58.6 mmol) of 2benzylthio-5-fluoromethyl-7-hydroxy-1,2,4- (prepared in Example B) and 100 ml of phosphorus oxychloride was heated at reflux for three hours and was then concentrated by simple distillation using a water aspirator to reduce the pressure to obtain a dark, viscous oil. This was dissolved in 300 ml of methylene chloride and treated cautiously with stirring with 200 ml of water. The mixture was stirred vigorously for 30 min. at ambient temperature and then allowed to separate into phases.
The organic phase was separated, washed with water and saturated aqueous sodium bicarbonate, dried over magnesium sulfate, and concentrated by evaporation under reduced pressure to obtain a dark oil. This solidified on trituration in hexane containing a little methylene chloride to yield 12.2 g (67 percent of theory) of the title compound as a tan solid melting at 81-86oC.
Elemental Analysis Calc. for C 13
H
10 C1FN 4 S: 50.57; 3.27; 18.14 Found: 51.14; 3.31; 13-23 1 WO 39/10368 PCT/US89/01547 -18- Example D. Preparation of 5-Fluoromethyl-7-chloro- 1,2,4-triazolo[r,5-a]pyrimidine-2-sulfonvl chloride A solution containing 10.0 g (32.4 mmol) of 2-benzylthio-5-fluoromethyl-7-chloro-1,2,4-triazolo- (prepared in Example C) in 100 ml of methylene chloride was combined with 100 ml of water and the mixture was cooled to 0-5 0 C. Gaseous chlorine was passed into the mixture for 45 min. with vigorous stirring and cooling so as to maintain a temperature of less than 8 0 C. The disappearance of starting material was monitored by reverse phase HPLC. The cold mixture was allowed to react for another 15 min.
and then the phases were allowed to separate and the 1 organic phase was removed, washed with water and aqueous sodium bisulfite, and dried over magnesium sulfate. The solvent was removed by evaporation to obtain the title compound as an oil, which on trituration in hexane containing a little methylene chloride solidified to a light brown powder that, after being collected and dried, amounted to 7.1 g (77 percent of theory) and melted at 92-98°C. The proton and fluorine nmr spectra were compatible with the assigned structure.
FINAL PRODUCTS Example 1. Preparation of 5-Fluoromethyl-7-methoxy- N-(2,6-dichlorophenyl)-1,2.4-triazolo-[1,5-alpyrimidine-2-sulfonamide A solution containing 3.08 g (13.1 mmol) of N-trimethylsilyl-2,6-dichloroaniline and 1.50 g (5.26 mmol) of 5-fluoromethyl-7-chloro-1,2,4-triazolo[1,5- i a]-pyrimidine-2-sulfonyl chloride (prepared in Example i ip 4 WO 89/10368 PCT/US89/01547 -19- D) in 15 ml of dry acetonitrile was prepared and 0.075 ml (1.05 mmol) of dimethyl sulfoxide was added with stirring at ambient temperature. The mixture was allowed to react over 4 days and the resulting brown solution was then diluted with 150 ml of methylene chloride, washed with water, and dried over magnesium sulfate. The solvent was removed by evaporation under reduced pressure and replaced with hexane to obtain, after collection of the solids and drying, 1.80 g (84 percent of theory) of the 7-chloro analog of the title compound in about 80 percent purity. This 7-chloro analog was dissolved in 25 ml of dry methanol, the solution cooled to 0-5°C and a mixture of 1.70 g (7.89 mmol) of 25 weight percent sodium methoxide in methanol and 5 ml of methanol was added dropwise with stirring over a 10 min. period.
The mixture was allowed to react for 10 min. and then about 1 ml of acetic acid was added. The solid that formed was collected, washed with methanol and with water, and dried to obtain 1.15 g (54 percent of theory) of the title compound as a light brown solid.
This was extracted by stirring in boiling methanol, cooling, collecting the solids, and drying to obtain 1.09 g of product melting at 189-191 0 C. The proton and fluorine nmr spectra were compatible with the assigned structure.
Elemental Analysis Calc. for C 13
H
10 C1 2
FN
5 O3S: 38.44; 2.48; 17.23 Found: 38.22; 2.70; 16.88 if ll WO 89/10368 PCr/US89/01547 Example 2 The following compounds were prepared in a similar way to the above procedure of Example 1 and found to have elemental analyses and proton and fluorine nmr spectra compatible with the assigned structures: 5-Fluoromethyl-7-m ethoxy-N- 6-difluorophenyl) 1, 2 4 -triazolo[1,5-alpyrimidine-2-sulfonamide, m.p.
161-165 0 C(dec); 5-Fluoromethyl-7-methylthio-N- 6-dIichlorophenyl) 1 ,2,4-triazolo[1 ,5-alpyrimidine-2-sulfonamide, m.p.
263-265 0 C(dec) thyl-7-me thoxy-N-[2-me thoxy-6, (trif luoromethyl)-phenyl]-1 ,2, 1 4-triazolo[l a~pyrimidine-2-sulfonamide, m.p. 170-172OC; 5-Fluoromethyl-7-methoxy-N-(2,6-dibromophenyl.1 ,2,4- -triazolo[1;5-alpyrimidine-2-sulfonamide, m.p. 184- 186’C; 255-Fluoromethyl-7-methylthio-N- 6-dibromophenyl) -raol[,-lyrmdn–sloaie m.p.
24112430C (dec); 5-Fluoromethyl-7-methoxy-N-( 2, 6-dichloro-3methylphenyl) -1 4-triazolo[ 1 ,5-a]pyrimidine-2sulfonamide, m.p. 198-201OC; and [1,5-alpyrimidine-2-sulfonamide, m.p. 215-218 0 C(dec) (by reduction with sodium cyanoborohydride).
i p ~L4 catalyst, such as dimethyl sulfoxide, and allowed to react at ambient temperature for several hours. The WO 89/10368 PCT/US89/01547 WO 89/10368 -21- Example 3. Preparation of (2,6-dichloro-3-methylphenyl)-1,2,4-triazolo[1,5-a1pyrimidine-2-sulfonamide A solution containing 6.78 g (27.3 mmol) of N-trimethylsilyl-2,6-dichloro-3-methylaniline and 3.11 g (10.9 mmol) of 5-fluoromethyl-7-chloro-1,2,4triazolo[1,5-a]pyrimidine-2-sulfonyl chloride in 25 ml of dry acetonitrile was prepared and 0.15 ml (2.2 mmol) of dimethyl sulfoxide was added with stirring at ambient temperature. The mixture was allowed to react for 4 days and the resulting brown solution was diluted with 150 ml of methylene chloride, washed with water and dried over magnesium sulfate. The Ssolvent was removed by evaporation under reduced pressure and replaced with hexane to obtain, after collection of the solids and drying, 3.7 g percent of theory) of the 7-chloro analog of the title compound in about 85 percent purity. A 1.85 g (4.36 mmol) portion of this was dissolved in 25 ml of dry ethanol and the solution cooled to 0-5 0 C and a mixture of 2.54 g (7.84 mmol) of 21 weight percent sodium ethoxide in ethanol and 7 ml of ethanol was added dropwise with stirring over a 15 min. period.
The mixture was allowed to .’eact for 10 min. and then about 1 ml of acetic acid was added and the combination poured into 50 ml of cold water. The solid that formed was collected, dried, extracted with ethanol, and redried to obtain 0.95 g percent of theory) of the title compound as a solid melting at 197-200°C. The proton and fluorine nmr spectra were compatible with the assigned structure.
I-i t WO 89/10368 PCT/US89/01547 -22- Elemental Analysis Calc. for C 15
H
14 C1 2
FN
5 0 3 S: 41.49; 3.25; 16.12 Found: 41.14; 3.25; 15.82 S Example I. Postemergence Herbicidal Activity Compounds of Formula were dissolved 4n 14 ml acetone and 1 ml of dimethyl sulfoxide at one half of the most concentrated desired application Sconcentration and the resulting solution was combined with 15 ml of an aqueous mixture containing about percent isopropyl alcohol, about 2 percent Atplus® 411F crop oil concentrate, and about 0.04 percent Triton® X-155 surfactant. Solutions containing lower concentrations were prepared by diluting this mixture with a solution containing equal parts of a mixture of the second component described above and acetone containing 3 percent dimethyl sulfoxide. The solutions of known concentration were sprayed evenly onto various greenhouse-grown plant species in approximately the 2-4 leaf stage by means of a hand sprayer so as to obtain total coverage. The treated plants and control plants were placed in a greenhouse and held under conditions conducive to growth. After 13 days the percentage of control compared to the untreated plants was determined visually.
Representative compounds tested, application rates employed, plant species tested, and results are given in Table I.
i TABLE I y N-N N -NHSO2 N C 2
F
POSTEMERGENCE HERBICIDAL ACTIVITY, PERCENT CONTROL Dose Morn- Wild Barny 1 12 R RtCot- WetCoffee Cockle- Jimson Lam- ing- Pig- Velvet- Buk ad Johnson- 111M o We br -We im glory we laf wheat Grass grass 0C1 1 3 C I I C1 125 100 100 100 100 10 100 1 00 100 I100 1 00 95 1 00 15.6 10 85 85 40 70 90 70 100 80 100 70 100 0C1 3 1; 11 Fi 125 50 g100 100 100 100 100 100 100 100 100 90 100 15.6 0 90 90 100 100 80 70 801 70 70 75 100 0C11 3 CIO. If C1 62. 100 j100 100 100 90 95 90 100 100 100 90 100 Lt3.9170150 -150150 80 95 70 80 80 90 60 TABLE I (cont’d) DY oR 2 j3 I Cot- Coffee Cockle- Jimson Lam- Morn- Pi Velvet- Johnson- Ra ton Wh Weed bur weed ium ng- weed leaf Buck- yard grass PPM ton Weed ur -weed glory wheat Grass grass OCI1 3 Br 11 Br 125 65 100 100 100 notest 100 100 100 90 100 100 100 15.6 0 90 90 80 no test 100 70 100 70 100 70 OC 1 3 Cl CIl 3 Cl 62.5 20 75 100 100 100 100 100 100 100 100 0 7.8 0 8 80 100 80 100 70 100 90 100 0 I1 F 11 F 125 80 55 0 100 100 100 80 100 100 80 20 15.6 0 30 0 80 100 100 0 90 70 no test 80
SCII
3 CI II Cl 62.5 90 70 100 100 100 50 80 100 80 90 50 SCIl 3 Br II Br 125 70 100 100 100 no test 100 100 100 80 100 100 100 1 5,6 15 60 100 30 no test 60 40 70 30 100 0 0
OC
2 11 Cl C11 3 Cl 62.5 100 90 100 100 100 100 100 100 100 100 30 40 0 90 100 40 100 70 90 70 100 0 00 0 0 -,1
J
fiI~MP.-to
T
t i’:d.SSS- RSSSSV&
V..
4.
r r 6 emerging seedlings and established vegetation.
PCr/US89/01547 WO 89/10368 Example II. Preemergence Herbicidal Activity Compounds of’ Formula were dissolved in ml of’ acetone at one half’ of’ the most concentrated desired application concentration and the resulting solution was combined with an equal volume of’ water containing 0.1 percent of’ TweenO 20 surfactant.
Solutions containing lower concentrations were prepared by diluting this with additional aqueous surfactant solution. The seeds of’ a number of’ species of’ plants were planted in beds containing a loam agricultural soil and, af’ter planting, predetermined amounts of’ the herbicide mixtures were sprayed on the soil surf’ace and watered in to achieve desired application rates. These and untreated control plants were then placed in a greenhouse under conditions conducive to germination and growth f’or a period of’ 14 days at which time a visual assessment was made of’ the reduction in stand and growth f’or the treated plants as compared to the control plants.
Representative compounds tested, application rates employed, plant species tested, and results are given in Table II.
1i TABLE II N NN )2 N N CH 2
F
PREEMERGENCE HERBICIDAL ACTIVITY, PERCENT CONTROL 1 1{2 R3 Rte, Cotton Wheat Curly Jimson Morning Pigweed Velvet- Barn- Johnson- Yellow R R g/Ha Dock -weed glory Pg leaf yard grass Foxg/Ha Grass tail OCH1 3 Cl II Cl 36 75 90 100 100 50 100 95 90 85 9) OCI1 3
CF’
3 11 OC11 3 36 85 100 85 80 50 100 90 100 95 100 OC11 3 Br II Br 140 65 100 no test no test 90 no test 95 90 85 98 OCl1 3 Cl C11 3 Cl 140 85 20 100 no test 75 80 95 0 0 36 0 0 90 no test 209 100 25 0 0 OCIl 3 F II F 140 90 100 100 100 60 100 85 90 75 100 SCIIs Cl II Cl 140 80 95 70 85 1 65 100 75 70 90 SC1i 3 Br Hl Br 310 85 100 no test no test 80 no test 80 85 85 OC.II Cl CII3 Cl 140 50 25 no test no test 100 100 95 0 0 70 35 0 no test no test 50 20 90 0 0 I Wo 89/10368 PCr/US89/01547 27- Example III. Soil Degradation Evaluation A sandy clay loanm soil from Davis, CA having a pH of about 7.3, a soil organic matter of about 1.6 percent, and consisting of about 50 percent sand, 26 percent silt, and 2 4 percent clay was employed. This soil was stored moist at about 13-16″‘C and was air dried and sifted in preparation for use. One hundred Sgram samples of this soil were placed in small plastic cups with no drain holes and treated with ml of water (sufficient water to bring the soil to about 80 percent of its field capacity) containing the quantity of test compound required to give the desired application rate. The solutions were prepared by dissolvilg the test compounds in a 97:3 acetone-dimethyl sulfoxide mixture and diluting with water. The application rates were recorded as ppm in the soil and 0.1 ppm in tile test is the equivalent of about 40 g/Ha. Enough cups were prepared to treat twelve sets of cups for each of three 3 incubation periods and each of five concentrations of each compound and for untreated controls. The cups were then capped with plastic lids containing an air hole about 3 mm in diameter and allowed to stand overnight at ambient temperature to equilibrate. Duplicate treatments were made for each concentration and sample time interval desired. Six replicates were ,V incubated in a 90-100 percent humidity room at about 27 0 C and the other six, the controls, were frozen.
After appropriate time periods, the cups were removed, planted with seven sunflower seeds (hybrid
I.
no. 3) as an indicator plant, and mulched with a very sandy soil. The cups were placed in a greenhouse i i under conditions conducive to germination and growth
L
‘H 1 V WO 89/10368 PCT/US89/01547 -28for 12-15 days. The plastic cups were then removed and the root growth evaluated visually on a scale of 0 to 20 wherein ratings are given as follows: 0= no root penetration of the treated soil; 1= up to 0.5 in. root penetration into treated soil; root penetration to the bottom of the treated soil including those with some slight bending at the bottom; 10= root penetration to the bottom of the treated soil with a loose network of roots at the bottom; root penetration so as to form roots throughout the soil mass and covering the bottom.
A phytotoxicity index for each incubated treatment, each frozen control, and each untreated control was then determined by adding together the ratings of the six replicates and dividing by six.
The percent of growth reduction was found for each compound at each concentration and each sampling time by applying the equation: 100x(phytotoxicity index of treatment phytotoxicity index of untreated control)/phytotoxicity index of untreated control.
The loss of herbicidal activity for each compound at each sampling period was then determined by plotting the percentage of growth reduction figures against the log of the initial concentration in the soil in ppm and finding the GR 50 (the amount of compound required to be applied for a 50 percent reduction in root growth after the stated time period) for each incubated compound and each frozen control at each sampling time. This data was converted to percentage loss of effectiveness of the herbicide due to soil degradation by application of the equation
‘I
J
W6 89/10368 PCI’/US89/O1 547 -29-
R
5 0 of incubated GR 5 0 of frozen control)/GR 5 0 of incubated. The half-life for degradation in the soil was the determined by application of the standard first-order rate equation. The half-lives obtained at the various times were averaged to obtain the reported values.
Half-lives under these conditions and using this method for the compounds of Formula I listed below were found to be less than 21 days.
5-Fluoromethyl-7-methoxy-N-(2, 6-dichlorophenyl)- 1 ,2,4-triazolo[1 ,5-alpyrimidine-2-sulfonamide, 155-Fluoromethyl-7-methoxy-N-(2,6-dichloro-3methylphenyl)-1,2, 1 4-triazolo(1,5-alpyrimidine-2sulfonamide, thyl -7-me thoxy-N-12-me thoxy-6 (trifluoromethyl)-phenyl]-1,2,4-triazolo[1 alpyrimidine-2-sulf onamide, 5-Fluoromethyl-7-methoxy-N-( 2, 6-difluorophenyl 1 ,2,4-triazolo[1 ,5-alpyrimidine-2-sulfonamide, 5-Fluoromethyl-7-methylthio-N-(2,6-dichlorophenyl)- 1 ,2,4-triazolo[1 ,5-alpyrimidine-2-.sulfonamide, and 5-Fluoromethyl-N-(2,6-difluorophenyl)-1,2,-triazolo.
[1 ,5-alpyrimidine-2-sulf onamide.
The half-life under these conditions and using this method for the compound of Formula (I) listed below was found to be less than 23 days.
(*4 WO 89/10368 PCT/US89/01 547 luoronethyl-N-( 2, 6-dichloro-3rethylphenyl)-1 ,2,4-tri4azolo[l ,5-alpyrimidine-2sulfonamide.
I

Claims (3)

1. A compound of the formula ~-NH-SO AN N H Y’ represents H, OH, Cl, CH 3 C 2 H 5 OCR 3 wherein: 0C 2 H 5 1 or SCH 3 C S S represents H, F, Cl, Br, CR CF30 NO 2 CO 2 (C 1 C 4 alkyl), or CON(C 1 -C 4 alkyl) 2 R 2represents R or CHR 3 and represents F, Cl, Br, NO 2 C 2 (C 1 -C 4 alkyl), CON(C 1 C 4 alkyl) 2 1 OCR 3 or OC 2 H 5 with the provisos a) that R1and R 3 are not S

4. *5 6 5* S S 6O** simultaneously NO 2 C 2 (C 1 -C 4 alkyl), or CON(C 1 4 alkyl 2 and b) that when R1and R 3 both represent F, Cl, or Br and Y’ is OC 2 H 5 1 R 2is CR 3 and agriculturally acceptable salts thereof. S 556S55 S S I II. 4 WO 8910368PCT/US89/01 547 -32- alkyl) 2 and R 2 is CH 3 when Y’ i 2 5 and R 1 and R 3 both represent FrBr and agriculturally ace ta;-b11-salts thereof.

52. A compound of Claim 1 wherein Y’ represents H, OCH 3 0C 2 H 5 or SCH 3 3. A compound of’ Claim 1 or 2 wherein R 1 represents F, Cl, Br, or CF 3 R 2 represents H or CH 3 and R 3 represents F, Cl, Br, or OCH 3 A compound of Claim 3 which is fluoromethyl-7-methoxy-N-(2,6-dichlorophenyl)j-i,2,4- triazololl, 5-al-pyrimidine-2-sulfonamide or an agriculturally acceptable salt thereof. A compound of Claim 3 which is fluoromethy1L-7-methoxy-N-:(2,6-difluorophenyl)-1 triazolo[1 ,5-al-pyrimidine-2-sulfonamide or an agriculturally acceptable salt thereof’. 6. A compound of Claim 3 which is fluoromethyl-7-methoxy-N-12-methoxy-6-( trifluoro- methyl)phenyll-1 4-triazolo[1 ,5-alpyrimidirie-2- sulfonamide or an agriculturally acceptable salt thereof’. 7. A compound of Claim 3 which is fluoromethyl-7-methoxy-N-(2,6-dichloro.-3-methylphenyl)- 1, 2 ,4-triazolo-[1,5-apyrimidine-2-sulfonamide or an agriculturally acceptable salt thereof. 8. A compound of Claim 3 which is fluoromethyl-7-methylthio-N-(2,6-dichlorophenyl).1 ,2,l4- 1 ,5-a]-pyrimidirie-2-sulfonamide or an agriculturally acceptable salt thereof’. Z W I virWO 89/10368 i PCr/US89/01547 -33- 9. A compound of Claim 3 which is fluoromethyl-N-(2,6-dichloro-3-methylphenyl)-1,2,4- triazolo[1,5-a]pyrimidine-2-sulfonamide or an agriculturally acceptable salt thereof. A process for preparing a compound of Formula as defined in Claim 1 which comprises reacting a compound of the formula Y’ N-N ClSO2 N N wherein Y’ is defined as in Claim 1, with a compound of the formula 1 -C 2 alkyl) 3 1′ wherein R 1 R 2 and R 3 are defined as in Claim 1, in an organic solvent with dimethylsulfoxide as a catalyst, then in a water immiscible solvent, and optionally separating the product of Formula 11. The process of Claim 10 which further comprises reacting a compound of Formula where Y’ .I F. WO 89/10368 PCT/US89/01547 -34- is Cl with sodium methoxide in methanol or sodium ethoxide in ethanol, at ambient temperature, followed by treating with acid and water to provide the compounds of Formula where Y’ is methoxy or ethoxy, respectively. 12. The process of Claim 10 which further comprises reacting a compound of Formula where Y’ is Cl with sodium methanethiolate in an alcohol, at ambient temperature, followed by treating with an acid and water to provide the compounds of Formula where Y’ is methylthio. 13. A composition containing an agriculturally acceptable adjuvant or carrier in combination with an herbicidally effective amount of a compound as claimed in any one of Claims 1 to 9 with the proviso that Y’ is other than OH or Cl. 14. A method of controlling unwanted vegetation which comprises applying to the vegetation or its locus an effective amount of a composition as claimed in Claim 13. 15. A method of controlling unwanted vegetation in crops which comprises applying to the crop or its locus a selectively effective amount of a composition of Claim 13. 16. A method according to Claim 15 wherein the crop is cotton or wheat. 17. A method according to Claim 15 wherein the compound is applied postemergently. i ii 1 i r A.dl 18. A compound of the formula Y T ANN N C 2 (II) wherein: Y or OCH 3 and T or ClSO 2 represents H, Cl, OH, CH 3 C 2 H 5 1, C 2 H 0 *0 0* 0 0 0 represents HS, (C 2 -C 4 alkyl)thio, benzylthio, 19. A compound of Claim 18 wherein T represents HS or benzylthio. 20. A compound of Claim 18 wherein T represents ClSO 2 21. A compound of Claim 19 or 20 wherein Y represents Cl, OH, or OCH 3 Pro*: 22. A compound of Claim 21 which is *0* .0 fluoromethyl-7–hydroxy-1,2,4-triazoo[1,5-.alpyrimidine. 23. A compound of Claim 21 which is fluoromethyl-7-chloro-1,2,4-triazolo41,5.ajpyrimidine. 24. A compound of Claim 21 which is 7 -chloro-1,2,4-triazolo[1,5-alpyrimidine-2sulfonyl chloride. A compound according to any one of the preceding claims substantially as herein described with reference to any one of the examples. ge lie- INTERNATIONAL SEARCH REPORT International Aoolicatlon No PCT/US 89, /01547 I CLASSIFICATION OF SUBJECT MATTER (it several classification symbols aooly, indicate all) According to International Patent Classification (IPC) or to both National Classification and IPC 4 IPC C 07 D 487/04, A 01 N 43/90 II. FIELDS SEARCHED Minimum Documentation Se rched 7 Classification System Classification Symbols IPC4 C 07 D 487/00 Documentation Searched other than Minimum Documentation to the Extent that such Documents are Included In the Flelds Searched 0 III. DOCUMENTS CONSIDERED TO BE RELEVANTI Category Citation of Document, with indication, where aoropriate, of the relevant passages I Relevant to Claim No. A EP, A, 0142152 (THE DOW CHEMICAL COMPANY) 1,10,13, 22 May 1985 18 see claims cited in the application A Chemical Abstracts, volume 67, 1967, 1,18 (Columbus, Ohio, US), R. Dohmori et al.: “Synthesis and antibacterial activity of fluorine- containing pyrimidinylsulfanilamide derivatives”, see page 8545, abstract 90760h, Yakugaku Zasshi 87(4), 419-29(1967) Special categories of cited documents: to later document published after the International filing date document defining the general state of the art which is not or priority date and not in conflict with the application but considered to be of particular relevance cited to unlritand the principle or theory underlying the invention earlier document but published on or aer the International document of particular relevance: the claimed Invention filing ate cannot be considered novel or cannot be considered to document which may throw doubts on priority claim(a) or involve an inventive step which Is cited to establish the publication date of another Y document f particular relevance; the clamed nvention citation or other aeDcial reason (aa ioeciiled) document of partlculer relevance! the claimed invention ittion or oer specia reaon pecie) cannot be considered to Involve an inventive step when the document referring to an oral disclosure, use, exhibition or document is combined with one or more other such docu- other means ments, such combination being obvious to a person skilled document published prior to the international filing date but in the art. later than the priority date claimed documen: member of the same patent family IV. CERTIFICATION Date of the Actual Completion of the International Search Date of Mailing o 1 hli nternatlonal Search Report 14th August 1989 J P. International Searching Authority Signature of red Ofn EUROPEAN PATENT OFFICE T.K. WILLIS Form PCT/ISA/210 (second aheet) (January 1915) i I, llllllh ic x i i ANNEX TO THE INTERNATIONAL SEARCH REPORT ON INTERNATIONAL PATENT APPLICATION NO. US 8901547 SA 28806 This annex lists the patent family members relating to the patent documents cited in the above-mentioned internationa; search report. The members are as contained in the European Patent Office Ef)P file on 06/09/89 The European Patent Office is in no way liable for these particulars which are merely given for th- rpo.a ;f informnation. Patent document Publication Patent family Publication cited in search report date member(s) date EP-A- 0142152 22-05-85 AU-A- AU-B- AU-A- CA-A- CA-C- CA-C- EP-A- GB-A,B GB-A,B GB-A,B JP-A- US-A- US-A- US-A- 2290088 583799 3533084 1231708 1232269 1232276 0330137 2149792 2196627 2196628 60116684 4740233 4741764 4755212 05-01-89 11-05-89 23-05-85 19-01-88 02-02-88 02-02-88 30-08-89 19-06-85 05-05-88 05-05-88 24-06-85 26-04-88 03-05-88 05-07-88 i I i- i; 1 j 4 I i-: i-i ij t _J I; .L- For more details about this annex see Official Journal of the European Patent Office, No. 12/82

AU36873/89A
1988-04-19
1989-04-13
5-fluoromethyl-1,2,4-triazolo(1,5-a)-pyrimidine-2- sulfonamides, process for their preparation and compositions for their use as herbicides

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1988-04-19
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7-ethoxy-5-fluoromethyl-1,2,4-triazole[1,5-a]-pyrimidine-2-sulfonamindes

US183571

1988-04-19

US183570

1988-04-19

US07/183,570

US4904301A
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1988-04-19
1988-04-19
5-Fluoromethyl-1,2,4-triazolo(1,5-A)-pyrimidines

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1988-03-11
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Bayer Aktiengesellschaft

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patent/DE68913338T2/en
not_active
Expired – Fee Related

1989-04-18
EP
EP89200980A
patent/EP0340828B1/en
not_active
Expired – Lifetime

1989-04-18
IL
IL90004A
patent/IL90004A/en
unknown

1989-04-18
CA
CA000596952A
patent/CA1331179C/en
not_active
Expired – Fee Related

1989-04-18
ES
ES89200980T
patent/ES2061935T3/en
not_active
Expired – Lifetime

1989-12-18
FI
FI896048A
patent/FI896048A0/en
not_active
Application Discontinuation

Patent Citations (2)

* Cited by examiner, † Cited by third party

Publication number
Priority date
Publication date
Assignee
Title

AU575372B2
(en)

1984-01-26
1988-07-28
Dow Chemical Company, The
Sulfonamides derived from substituted 2-amino-1,2,4- triazolo (1,5-a) pyrimidines

AU3126589A
(en)

1988-03-11
1989-09-14
Bayer Aktiengesellschaft
Triazolo pyrimidine-2-sulphonamides

Also Published As

Publication number
Publication date

CA1331179C
(en)

1994-08-02

JPH02503924A
(en)

1990-11-15

ES2061935T3
(en)

1994-12-16

WO1989010368A1
(en)

1989-11-02

IL90004A0
(en)

1989-12-15

IL90004A
(en)

1993-07-08

EP0340828A1
(en)

1989-11-08

FI896048A0
(en)

1989-12-18

DE68913338D1
(en)

1994-04-07

AU3687389A
(en)

1989-11-24

EP0340828B1
(en)

1994-03-02

BR8906918A
(en)

1990-11-13

HU893303D0
(en)

1990-07-28

HUT52916A
(en)

1990-09-28

DE68913338T2
(en)

1994-06-09

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