CA1266667A - Herbicidal aryl triazolinones - Google Patents
Herbicidal aryl triazolinonesInfo
- Publication number
- CA1266667A CA1266667A CA000493598A CA493598A CA1266667A CA 1266667 A CA1266667 A CA 1266667A CA 000493598 A CA000493598 A CA 000493598A CA 493598 A CA493598 A CA 493598A CA 1266667 A CA1266667 A CA 1266667A
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- Prior art keywords
- methyl
- compound
- alkyl
- dihydro
- phenyl
- Prior art date
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
- C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
- C07D409/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Plural Heterocyclic Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE:
Herbicidal aryl triazolinones include the com-pounds of the formula where X is preferably halogen such as fluorine, Y is preferably halogen such as chlorine, R1 is prefer-ably methyl, R2 is preferably CHF2, R3 is pre-ferably CH(CH3). Z is oxygen or sulfur. R4 may be alkyl, substituted alkyl, alkenyl, alkynyl, mono-valent cyclic having a ring of 5 or 6 atoms or ZR4 may be a residue of an amine, a sulfonamide. or an oxime.
0832W0082Wmd
Herbicidal aryl triazolinones include the com-pounds of the formula where X is preferably halogen such as fluorine, Y is preferably halogen such as chlorine, R1 is prefer-ably methyl, R2 is preferably CHF2, R3 is pre-ferably CH(CH3). Z is oxygen or sulfur. R4 may be alkyl, substituted alkyl, alkenyl, alkynyl, mono-valent cyclic having a ring of 5 or 6 atoms or ZR4 may be a residue of an amine, a sulfonamide. or an oxime.
0832W0082Wmd
Description
-~66~6~
Docket 4579 HERBICIDAL ARYL TRIAZOLINONES
- The invention described in this application per-tains to weed control in agriculture, horticulture, and other fields where there is a desire to control unwanted plant growth. More specifically, the present application describes certain herbicidal aryl tria-zolinones, compositions of them, methods of preparing them, and methods for preventing or destroying unde-sired plant growth by preemergence or postemergence application of the herbicidal compositions to the locus where control is desired. The present compounds may be used to effectively control a variety of both grassy and broadleaf plant species. The presene invention is partic-ularly useful in agriculture; a 1 15 number of the compounds described herein show a selec-~' tivity ~avorable to certain crops at applicati`on levels which inhibit the growth of or destroy a variety of weeds.
One aspect of this invention relates to herbici-'~ 20 dal compounds of the general formula ., ~
:, X O
Y ~ N ~ Rl (Formula I) R3CooR4 wherein R is CHF2 or CH2F;
; X is~bromine, chlorin~e, or~fluorine or haloalkyl e.g. CF3);
Rl~may be halogen (e.g. chlorine), alkyl (e.g.
25~ of l to 5 carbon atoms), haloalkyl (e.g. of l~to 5 carbon atoms such as difluoromethyl), alkoxyalkyl te.~g. of~2 to~6 carbon atoms such as methoxymethyl), cyanoalkyl~(e.~g. of 2 to 6~carbon atoms such as cyano-mcthyl), arylalkyl such as benzyl, alkylthio ~e.g. of 1 to 3 carbon atoms such as methylthio) or the corre-sponding al~ylsul~inyl or alkylsulfonyl, or alkylthio-alkyl (e.g., of 1 to 3 carbon atoms independently ~ith respect to each alkyl, such as methylthiomethyl) or the corresponding alkylsulfinylalkyl or alkylsulfonyl-alkyl.
Y is bromine, chlorine, ~luorine, methyl, haloalkyl (e.g. FCH ), a radical of the ~ormula R80CH2-, R8SCH2-, R~SOCH2- or R8S02CH2-where R is Cl-C3alkyl, C2-C5alkenyl, or C3-C5 alkynyl (e.g., CH30CH2-, CH3SCH2-, CH2=CHCH20CH2-,
Docket 4579 HERBICIDAL ARYL TRIAZOLINONES
- The invention described in this application per-tains to weed control in agriculture, horticulture, and other fields where there is a desire to control unwanted plant growth. More specifically, the present application describes certain herbicidal aryl tria-zolinones, compositions of them, methods of preparing them, and methods for preventing or destroying unde-sired plant growth by preemergence or postemergence application of the herbicidal compositions to the locus where control is desired. The present compounds may be used to effectively control a variety of both grassy and broadleaf plant species. The presene invention is partic-ularly useful in agriculture; a 1 15 number of the compounds described herein show a selec-~' tivity ~avorable to certain crops at applicati`on levels which inhibit the growth of or destroy a variety of weeds.
One aspect of this invention relates to herbici-'~ 20 dal compounds of the general formula ., ~
:, X O
Y ~ N ~ Rl (Formula I) R3CooR4 wherein R is CHF2 or CH2F;
; X is~bromine, chlorin~e, or~fluorine or haloalkyl e.g. CF3);
Rl~may be halogen (e.g. chlorine), alkyl (e.g.
25~ of l to 5 carbon atoms), haloalkyl (e.g. of l~to 5 carbon atoms such as difluoromethyl), alkoxyalkyl te.~g. of~2 to~6 carbon atoms such as methoxymethyl), cyanoalkyl~(e.~g. of 2 to 6~carbon atoms such as cyano-mcthyl), arylalkyl such as benzyl, alkylthio ~e.g. of 1 to 3 carbon atoms such as methylthio) or the corre-sponding al~ylsul~inyl or alkylsulfonyl, or alkylthio-alkyl (e.g., of 1 to 3 carbon atoms independently ~ith respect to each alkyl, such as methylthiomethyl) or the corresponding alkylsulfinylalkyl or alkylsulfonyl-alkyl.
Y is bromine, chlorine, ~luorine, methyl, haloalkyl (e.g. FCH ), a radical of the ~ormula R80CH2-, R8SCH2-, R~SOCH2- or R8S02CH2-where R is Cl-C3alkyl, C2-C5alkenyl, or C3-C5 alkynyl (e.g., CH30CH2-, CH3SCH2-, CH2=CHCH20CH2-,
2 2 2 , CH-CCH2OCH2-, or CH-C-CH SCH
R8 may also be phenyl (or phenyl substituted with e.g., halogen, alkyl, haloalkyl; see, e.g. compound 50, below~.
R is an alkylene radical (e.g. a lower alkyl-ene such as -CH2- or -CH(CH3)-) or a haloalkylene ~ radical (e.g. -CHF-) and R is an alkyl radical ;~ 20 (e.g. CH3, C2H5~ C3H7~ C4Hg). 2 It is preferred that R be methyl and R be -~ CHF2 and particularly that X be chlorine or (more preferably) fluorine and Y be chlorine.
Some of the compounds described above difer from 2~5 otherwise similar compounds~disclosed in U.S. patent 4,318,731 in that ~ of that patent is hydrogen, an ~ alkyl group, or an alkenyl group. It has been ~ound `~ now that the replacement of an alkyl group by a CHF2 or CH2F group yields compounds of much greater herbicidal activity. This is shown, for instance, in Table I below which gives~the~results of tests of the ;following;two compounds,~each applied at the rate of 0.125 kg. per hectare: ~
A. A compound in which R2 is CHF2 . ~
: .
. . .;.. ,~ .;
R8 may also be phenyl (or phenyl substituted with e.g., halogen, alkyl, haloalkyl; see, e.g. compound 50, below~.
R is an alkylene radical (e.g. a lower alkyl-ene such as -CH2- or -CH(CH3)-) or a haloalkylene ~ radical (e.g. -CHF-) and R is an alkyl radical ;~ 20 (e.g. CH3, C2H5~ C3H7~ C4Hg). 2 It is preferred that R be methyl and R be -~ CHF2 and particularly that X be chlorine or (more preferably) fluorine and Y be chlorine.
Some of the compounds described above difer from 2~5 otherwise similar compounds~disclosed in U.S. patent 4,318,731 in that ~ of that patent is hydrogen, an ~ alkyl group, or an alkenyl group. It has been ~ound `~ now that the replacement of an alkyl group by a CHF2 or CH2F group yields compounds of much greater herbicidal activity. This is shown, for instance, in Table I below which gives~the~results of tests of the ;following;two compounds,~each applied at the rate of 0.125 kg. per hectare: ~
A. A compound in which R2 is CHF2 . ~
: .
. . .;.. ,~ .;
- 3 (compound No. 5 described below).
B. An otherwise identical compound in which R is C2H5 (compound 62 of the aforesaid U.S.
patent).
Representative compounds according to this aspect of the invention are given in Table 2 below.
The herbicidal esters of the aspect of the inven-tion described above may be hydrolyzed to produce the corresponding acids, i.e., to compounds of the fore-going formula in which the substituent-para to "X" is -OR COOH (i.e. carboxyalkoxy). I have found that these acids are also effective herbicides, somewhat less potent than the corresponding esters. The acids are also useful as intermediates for the preparation (as by esteriication or amide formation) of other herbicidal compounds. The acids may be converted to their salts,.such as their sodium, potassium, ammo-nium, calcium, magnesium, or mono, di or trialkylammo-nium sal~s, which may be used as herbicides.
Representative acids and salts are shown in Table 3 below.
;~ In another aspect of this invention it has now been found that compounds of the following formula are effPctive herbicidal compounds:
X o (For~ula II~
oR~cozR
i: :
25~ wherein~R4 is a substituted alkyl group, an alkenyl group~(e.g. allyl or methallyl) or an alkynyl group (e.g., propargyl) or a monovalent cyclic group having a ring o~ 5 or 6 atoms te.g. an aromatic or hetero-,.. ~. , , . ~ : ,. . :
. : :.; . . :
'' :' ~
cyclic or alicyclic ring) whose valence is on a carbon atom of said ring, and Z is 0 or S. Corresponding compounds in which Z is su~lfur and R4 is unsubsti-tuted alkyl (e.g. of 1-4 carbon atoms) have also been found to be effective herbicides. With respect to ~4, examples of suitable substituents on the alkyl group are:
; nitro;
halo (Cl,F,Br);
furyl or tetrahydrofuryl;
acetyl (CH3C0);
C0 N(RII)(RIII) where -N{RII)(RII ) is the residue (minus hydrogen) of ammonia or of a pri-mary or secondary amine (e.g. methylamine, dimethyl-amine or other lower alkylamine);
- cyano;
-COORIV where RIV is the residue of an alco-hol (such as the residue o~ a lower alkanol, e.g. a methyl or ethyl radical);
phenyl or substituted phenyl;
alkylamino, dialkylamino or a trialkylammor.ium salt (such as that shown in compound no. B20 below);
- alkoxy, alkylthioj alkylsulfinyl or alkylsul~onyl (in which radicals the alkyl is preferaby methyl or other lower alkyl~ or phenoxy, phenylthio, phenylsul-finyl, or phenylsulfonyl (in which radicals the phenyl moiety may be substituted or unsubstituted).
When R4 is alkenyl or alkynyl it may be substi-tuted with one of the foregoing substituents.
For the substituted phenyls mentioned above the substituents may be, for instance, alkyl, haloalkyl, ` aIkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, halogen, cyano, nitro, hydroxy, amino or alkyl or dialkylamlno or carboxyl.
It is preferred that X, Y, Rl and RZ be as .
, , ~
: :
. - ......
, ~ .
, ~L2~
de~ined above for Formula I, and particularly that X
be chlorine or (more preferably) fluorine, Y be chlo-rine, Rl be methyl and R be CHF2. However, within the broader scope of this aspect of the inven-tion R2 substituents may be alkyl te.g. of 1 to 5 carbon atoms), haloalkyl (e.g. of 1 to 5 carbon atoms, such as CHF2), alkenyl of 2 to 5 carbon atoms (e.g.
allyl), alkynyl oE 3 to 5 carbon atoms (e.g. pro-pargyl), cyanoalkyl (e.g. CH2CN or CH2CH2CN), thio-cyanoalkyl (e.g. CH2SCN) or a group of the formula -alkylene-Yl-R5 in which said alkylene group (e.g.
-CH2-) has 1 to 5 carbon atoms, yl being oxygen or S()r in which r is 0 to 2, and R being alkyl (e.g. of 1 to 5 carbon atoms such as methyl), alkenyl of 2 to 5 carbon atoms (e.g. allyl) or alkynyl of 3 to 5 carbon atoms (such as propargyl).
Representative compounds according to this aspect of the invention are shown in Table 4 below.
In still another aspect of this invention i.t has now been found that compounds of the following formula are efEective herbicidal compounds:
, ~ .
~ :~ X NJ;~N82 (Fo:m~l~
R3CoN~ 7 :: .
in whlch R3 is an alkylene~radical (e.g. -CH2- or CH(CH3)-) or a haloalkylene radical (e.g. -CHF-), , , . : ~ i :- - ~ :. . , , ,~; , ~: : : : :
c~7 ~ R
and -N~ 7is -NH2 or the residue of a primary or : R
secondary amine or of a sulfonamide. For instance, R6 and R7 may be, each, indèpendently, H, alkyl, alkenyl, alkynyl, cycloalkyl, aryl, alkoxy, alkylsul-~onyl, haloalkylsul~onyl, cycloalkylsulfonyl, arylsul-fonyl (including heteroarylsulfonyl such as thienyl-sul~onyl), aralkylsulfonyl, aminosulfonyl, dialkyl-aminosulEonyl, alkylaminosulfonyl, alkenylsulfonyl, phenylalkenylsulfonyl. R6 may be bicyclic or poly-cyclic such as benzofuranyl, dihydrobenzofuranylbenzo~uransulfonyl, dihydrobenzofuransulfonyl, naphthalenesulfonyl, benzodioxosulfonyl, anthraquin-- onesul~onyl. Any of R6, R7 may carry one or more substituents such as halogen, nitro, amino, alkoxy, alkyl, haloalkoxy, alkenyloxy, haloalkenyloxy, alkoxy-~- allcoxy, alkoxyalkylthio, cyano, aminocarbonyloxy, alkylaminocarbonyloxy or dialkylaminocarbonyloxy, acylamino, alkoxycarbonyl, aminocarbonyl, alkylamino-carbonyl, dialkylaminocarbonyl or hydroxycarbonyl (but 2;0 when one of R6, R7 is connected to the nitrogen of `; ~ormula III by an oxygen or sulfur atom, then the other oÇ R ~, R is H or~a group connected to that nitrogen by a carbon-nitrogen linkage or a salt-form-ing group, such as indicated below). R6 and R7 may together c~omprise a divalent group, such as an alkylene or haloalkylene or alkyloxyalkylene group or thi~oether, or its corresponding sulfine or sulfone, e.g. such that NR6R7 tog~ether comprise a pyrroli-dino, piperidino, morpholino, or thiazolidino ring), an~y of which may~also carry~a carboxylic ester or amide substituent. The salt-forming group (e.g. when R6 is alkylsul~onyl, cycloalkylsulfonyl or aryl-sulfonyl~ may b~e a metai (e.g. Na,~K or Ca) or ammo-:: . : ,:; . ,:. ,, ;~, : , ,., :
-: . . :: ,. . .
~26~ 7 nium (e.g. NH4 or lower alkyl-substituted ammo~
nium). R6 and R may comprise a divalent group such that NR R together constitute, for instance, a saccharin ring structure, e.g. ~ ~ which is an active herbicide (such as compound C62 below) and which upon hydrolysis, can lead to other active herbi-cides such as compounds C58 and C59.
Compound C62 for example is obtainable by reac-o tion of saccharin H~ ~ with the appropriate acid chloride.
In this (Formula III) aspect of the invention, ~, Y and P~ may be as de~ined above for Formula Ij and R may be as defined above for Formula II. It is preferred that R be methyl and R ~be CHF2 and particularly that X be chlorine or (more preferably) fluorine and Y be chlorine.
:, ~ Representative compounds according to this aspect -: ~ of the invention are shown in Table 5 below.
Still ano~ther aspect of this inventlon relates to 20~` ~herbicidal compounds of the~ formula -: : :
. ~ :
(F~r=L1~ IV) ~S~7 where -OR9 is the residue of an oxime, such as a ~ alkyl S-alkyl ketoxlme of the formula IIO-N=C~ 1 or HO N C~ alkyl each alkyl group preferably being lower alkyl such as methyl. X, Y, Rl and R have the meanings given in connection with Formula I ~for X, Y and Rl) and Formula II (for R2). Preferably X is chlorine or (more pre~erably) fluorine, Y is chlorine, Rl is methyl and R2 is CHF2; in some typical compounds of this kind the radical oR3C00R9 is -OCH~CH3)C0ON=C
/ SCH3 ~CH3 or -OCH(CH3)COON=C , X is fluorine, Y is \ C~I
chlorine, Rl is methyl and R is CHF2; other - typical compounds are identical with those except~ that Y is Br or CF3. Compounds of Formula IV may be ~; prepared by reacting the corresponding acid chloride (i.e. ~he compound in which the substituent at the 5-position of the benzene ring is -OR3COCl) with the corresponding oxime in the presence of an acceptor for HCl such as triethylamine or sodium carbonate or sodium hydroxide. ~ ~
;~ ~ 20 ~ In each aspect of the invention, it is often pre-ferable that any alkyl, alkenyl, alkynyl or alkylene radical have less than 6 carbon atoms.
The compounds of this lnvention may be prepared by~method~s generally described in ;the literature or by 25 ~ methods analogous~or similar thereto and within the;
sklll of the art.~ One type~ of me~thod starts with an intermediate in~which the s;ubstituent para to "X" is hydroxyl.~ For instance, one may use the intermediate descrlbed ln "Synthetic Proces~s~Example 6" of UX
30~ ~ ~pa~tent applicatlon GB 2 090 250 published 7 July 1982, : . ~ ~ ~ , . ...
in which X and Y are Cl, Rl is CH3 and R is CHF2 (the corresponding compound in which R2 is CH2F is made by substituting chlorofluoromethane for the chlorodifluoromethane used in "Synthetic Process Example 1" o~ that published patent application). The OH group of the intermediate may then be converted to the desired substituent, as by a conventional etheri-~ication reaction, e.g., by reacting it with the appropriate bromide in the presence of a known accep-tor of HBr such as NaH or a mixture of K2C03 and NaI.
As illustrated in ~xamples 2 and 3 below, the synthesis may employ a substituted phenylhydrazine, whose hydrazine portion is then modified to ~orm a triazolinone ring. Such modification (which in ~; Examples 2 and 3 is ef~ected by reaction with pyruvic acid and then with a phosphoryl azide) may also be ~- effected by other techniques, such as by treating the substituted phenylhydrazine with any of the folIowing ~our types of reagents:
(a) an inner salt of a 3~ iminoalkylmer-capto)-l-propanesulfonic acid twhich may be prepared according to Reid and Schmidt, Ann. Chem. 676, 114 (1964) ~rom 1,3-propanesultone and a thioamide), to form an amidrazone followed by reaction with a source of phosgene, as by the following reaction sequence ~;~ (which is also illustrated in~Example 15~below), r ~ ~Z : ~20 ~ R2 CR3C-6--S03 ArNHNH2 ~ ArN~-ND~ --> ArNR-N~
E'cO~I ~ C~3; ~ 3 o HS~--503H amidr~zone oluen~ ~ ~U~ "Salt"
Ar-N N-H
13COCOCl ~ ..
:~Z~$~ 7 in which "Ar" is aro~atic as described below.
~b) An i~idate ester of the formula Cl~
RCC-oRd to form the corresponding amidrazone (as described, for instance, in the article by Neilson et al "The Chemistry of Amidrazones: Chem. Rev. 70, 151(1970j at ~ page 156), followed by reaction with a source of phos-; gene, as in (a) above, Rc and Rd being alkyl or other suitable radical.
(c) A compound of the formula , 3 C~3 RaO-c=N~ooRb or RaSC=NCOOR~
(where Ra and Rb are lower alkyl) in the presence of a base according to the following sequence:
l O
~C-NCOORb ~ ArNEN~2 - > ~Ar-N N-H
n~whl~h~R~ eJ de~lned~abovQ, e.q. methyl;
(d)~ A haloalkylnitrile (e.g. a fluoroalkyl, fluorochloroalkyl or fluorobromoalkyl nitrlle such as Cl~CF2CN, ~followed by reacti~on~with a sourc;e~ of phos-~
gene,~so that the reaction may proceed along ~the ;following~lines, for instance (and as als;o~illustrated 2~0 ~ in~Example 1~6 below), to form the aryl 3-haloalkyl r~aioli~- ~hus~
: ~ - , , : :
,. : ~ ~ - ~ . .- .: - :
~rNHNH2 ~ ClC~2CN ~ N-C-C~2Cl ~ --> A~-N~ N-~3 C~30H Cl~COCCl CF2 or COC12 In Examples 2 and 3 below the "Ar" portion of the aryl hydrazine (whose hydrazine portion is then modi-fied to form the triazoline ring) has halo substi-tuents at its 2 and 4 positions and an alkoxy group atits S position. Instead, in each of the processes illustrated above (and in the process of those Examples 2 and 3), the Ar group may be a phenyl ~; radical or a fluorophenyl ~e.g. Z-fluorophenyl) or a nitrophenyl (e.g. 3-nitrophenyl) alkoxyphenyl (e.g.
3-methoxyphenyl) or, most preferably, halonitrophenyl, - ~ particularly a fluoronitrophenyl (such as 2-fluoro-S-~- nitrophenyl) or haloalkoxyphenyl (such as 2-fluoro-5-alkoxyphenyl) and the aryl triazoline may then be treated to (a) alkylate the nitrogen at the 4-position of the triazoline ring (in known manner, e.g. with an alkyl or fluoroalkyl halide, such as with ClCHF2 to add the preferred - CHFz substituent) and (b) to introduce additional substituents onto the aro~atic 2Q r~ing, as by~halogenation wi~th chlorine or bromine (e.g. by reacting with C12~,~Brz~or SO2C12).
For instance the alkylation of the nitrogen at the
B. An otherwise identical compound in which R is C2H5 (compound 62 of the aforesaid U.S.
patent).
Representative compounds according to this aspect of the invention are given in Table 2 below.
The herbicidal esters of the aspect of the inven-tion described above may be hydrolyzed to produce the corresponding acids, i.e., to compounds of the fore-going formula in which the substituent-para to "X" is -OR COOH (i.e. carboxyalkoxy). I have found that these acids are also effective herbicides, somewhat less potent than the corresponding esters. The acids are also useful as intermediates for the preparation (as by esteriication or amide formation) of other herbicidal compounds. The acids may be converted to their salts,.such as their sodium, potassium, ammo-nium, calcium, magnesium, or mono, di or trialkylammo-nium sal~s, which may be used as herbicides.
Representative acids and salts are shown in Table 3 below.
;~ In another aspect of this invention it has now been found that compounds of the following formula are effPctive herbicidal compounds:
X o (For~ula II~
oR~cozR
i: :
25~ wherein~R4 is a substituted alkyl group, an alkenyl group~(e.g. allyl or methallyl) or an alkynyl group (e.g., propargyl) or a monovalent cyclic group having a ring o~ 5 or 6 atoms te.g. an aromatic or hetero-,.. ~. , , . ~ : ,. . :
. : :.; . . :
'' :' ~
cyclic or alicyclic ring) whose valence is on a carbon atom of said ring, and Z is 0 or S. Corresponding compounds in which Z is su~lfur and R4 is unsubsti-tuted alkyl (e.g. of 1-4 carbon atoms) have also been found to be effective herbicides. With respect to ~4, examples of suitable substituents on the alkyl group are:
; nitro;
halo (Cl,F,Br);
furyl or tetrahydrofuryl;
acetyl (CH3C0);
C0 N(RII)(RIII) where -N{RII)(RII ) is the residue (minus hydrogen) of ammonia or of a pri-mary or secondary amine (e.g. methylamine, dimethyl-amine or other lower alkylamine);
- cyano;
-COORIV where RIV is the residue of an alco-hol (such as the residue o~ a lower alkanol, e.g. a methyl or ethyl radical);
phenyl or substituted phenyl;
alkylamino, dialkylamino or a trialkylammor.ium salt (such as that shown in compound no. B20 below);
- alkoxy, alkylthioj alkylsulfinyl or alkylsul~onyl (in which radicals the alkyl is preferaby methyl or other lower alkyl~ or phenoxy, phenylthio, phenylsul-finyl, or phenylsulfonyl (in which radicals the phenyl moiety may be substituted or unsubstituted).
When R4 is alkenyl or alkynyl it may be substi-tuted with one of the foregoing substituents.
For the substituted phenyls mentioned above the substituents may be, for instance, alkyl, haloalkyl, ` aIkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, halogen, cyano, nitro, hydroxy, amino or alkyl or dialkylamlno or carboxyl.
It is preferred that X, Y, Rl and RZ be as .
, , ~
: :
. - ......
, ~ .
, ~L2~
de~ined above for Formula I, and particularly that X
be chlorine or (more preferably) fluorine, Y be chlo-rine, Rl be methyl and R be CHF2. However, within the broader scope of this aspect of the inven-tion R2 substituents may be alkyl te.g. of 1 to 5 carbon atoms), haloalkyl (e.g. of 1 to 5 carbon atoms, such as CHF2), alkenyl of 2 to 5 carbon atoms (e.g.
allyl), alkynyl oE 3 to 5 carbon atoms (e.g. pro-pargyl), cyanoalkyl (e.g. CH2CN or CH2CH2CN), thio-cyanoalkyl (e.g. CH2SCN) or a group of the formula -alkylene-Yl-R5 in which said alkylene group (e.g.
-CH2-) has 1 to 5 carbon atoms, yl being oxygen or S()r in which r is 0 to 2, and R being alkyl (e.g. of 1 to 5 carbon atoms such as methyl), alkenyl of 2 to 5 carbon atoms (e.g. allyl) or alkynyl of 3 to 5 carbon atoms (such as propargyl).
Representative compounds according to this aspect of the invention are shown in Table 4 below.
In still another aspect of this invention i.t has now been found that compounds of the following formula are efEective herbicidal compounds:
, ~ .
~ :~ X NJ;~N82 (Fo:m~l~
R3CoN~ 7 :: .
in whlch R3 is an alkylene~radical (e.g. -CH2- or CH(CH3)-) or a haloalkylene radical (e.g. -CHF-), , , . : ~ i :- - ~ :. . , , ,~; , ~: : : : :
c~7 ~ R
and -N~ 7is -NH2 or the residue of a primary or : R
secondary amine or of a sulfonamide. For instance, R6 and R7 may be, each, indèpendently, H, alkyl, alkenyl, alkynyl, cycloalkyl, aryl, alkoxy, alkylsul-~onyl, haloalkylsul~onyl, cycloalkylsulfonyl, arylsul-fonyl (including heteroarylsulfonyl such as thienyl-sul~onyl), aralkylsulfonyl, aminosulfonyl, dialkyl-aminosulEonyl, alkylaminosulfonyl, alkenylsulfonyl, phenylalkenylsulfonyl. R6 may be bicyclic or poly-cyclic such as benzofuranyl, dihydrobenzofuranylbenzo~uransulfonyl, dihydrobenzofuransulfonyl, naphthalenesulfonyl, benzodioxosulfonyl, anthraquin-- onesul~onyl. Any of R6, R7 may carry one or more substituents such as halogen, nitro, amino, alkoxy, alkyl, haloalkoxy, alkenyloxy, haloalkenyloxy, alkoxy-~- allcoxy, alkoxyalkylthio, cyano, aminocarbonyloxy, alkylaminocarbonyloxy or dialkylaminocarbonyloxy, acylamino, alkoxycarbonyl, aminocarbonyl, alkylamino-carbonyl, dialkylaminocarbonyl or hydroxycarbonyl (but 2;0 when one of R6, R7 is connected to the nitrogen of `; ~ormula III by an oxygen or sulfur atom, then the other oÇ R ~, R is H or~a group connected to that nitrogen by a carbon-nitrogen linkage or a salt-form-ing group, such as indicated below). R6 and R7 may together c~omprise a divalent group, such as an alkylene or haloalkylene or alkyloxyalkylene group or thi~oether, or its corresponding sulfine or sulfone, e.g. such that NR6R7 tog~ether comprise a pyrroli-dino, piperidino, morpholino, or thiazolidino ring), an~y of which may~also carry~a carboxylic ester or amide substituent. The salt-forming group (e.g. when R6 is alkylsul~onyl, cycloalkylsulfonyl or aryl-sulfonyl~ may b~e a metai (e.g. Na,~K or Ca) or ammo-:: . : ,:; . ,:. ,, ;~, : , ,., :
-: . . :: ,. . .
~26~ 7 nium (e.g. NH4 or lower alkyl-substituted ammo~
nium). R6 and R may comprise a divalent group such that NR R together constitute, for instance, a saccharin ring structure, e.g. ~ ~ which is an active herbicide (such as compound C62 below) and which upon hydrolysis, can lead to other active herbi-cides such as compounds C58 and C59.
Compound C62 for example is obtainable by reac-o tion of saccharin H~ ~ with the appropriate acid chloride.
In this (Formula III) aspect of the invention, ~, Y and P~ may be as de~ined above for Formula Ij and R may be as defined above for Formula II. It is preferred that R be methyl and R ~be CHF2 and particularly that X be chlorine or (more preferably) fluorine and Y be chlorine.
:, ~ Representative compounds according to this aspect -: ~ of the invention are shown in Table 5 below.
Still ano~ther aspect of this inventlon relates to 20~` ~herbicidal compounds of the~ formula -: : :
. ~ :
(F~r=L1~ IV) ~S~7 where -OR9 is the residue of an oxime, such as a ~ alkyl S-alkyl ketoxlme of the formula IIO-N=C~ 1 or HO N C~ alkyl each alkyl group preferably being lower alkyl such as methyl. X, Y, Rl and R have the meanings given in connection with Formula I ~for X, Y and Rl) and Formula II (for R2). Preferably X is chlorine or (more pre~erably) fluorine, Y is chlorine, Rl is methyl and R2 is CHF2; in some typical compounds of this kind the radical oR3C00R9 is -OCH~CH3)C0ON=C
/ SCH3 ~CH3 or -OCH(CH3)COON=C , X is fluorine, Y is \ C~I
chlorine, Rl is methyl and R is CHF2; other - typical compounds are identical with those except~ that Y is Br or CF3. Compounds of Formula IV may be ~; prepared by reacting the corresponding acid chloride (i.e. ~he compound in which the substituent at the 5-position of the benzene ring is -OR3COCl) with the corresponding oxime in the presence of an acceptor for HCl such as triethylamine or sodium carbonate or sodium hydroxide. ~ ~
;~ ~ 20 ~ In each aspect of the invention, it is often pre-ferable that any alkyl, alkenyl, alkynyl or alkylene radical have less than 6 carbon atoms.
The compounds of this lnvention may be prepared by~method~s generally described in ;the literature or by 25 ~ methods analogous~or similar thereto and within the;
sklll of the art.~ One type~ of me~thod starts with an intermediate in~which the s;ubstituent para to "X" is hydroxyl.~ For instance, one may use the intermediate descrlbed ln "Synthetic Proces~s~Example 6" of UX
30~ ~ ~pa~tent applicatlon GB 2 090 250 published 7 July 1982, : . ~ ~ ~ , . ...
in which X and Y are Cl, Rl is CH3 and R is CHF2 (the corresponding compound in which R2 is CH2F is made by substituting chlorofluoromethane for the chlorodifluoromethane used in "Synthetic Process Example 1" o~ that published patent application). The OH group of the intermediate may then be converted to the desired substituent, as by a conventional etheri-~ication reaction, e.g., by reacting it with the appropriate bromide in the presence of a known accep-tor of HBr such as NaH or a mixture of K2C03 and NaI.
As illustrated in ~xamples 2 and 3 below, the synthesis may employ a substituted phenylhydrazine, whose hydrazine portion is then modified to ~orm a triazolinone ring. Such modification (which in ~; Examples 2 and 3 is ef~ected by reaction with pyruvic acid and then with a phosphoryl azide) may also be ~- effected by other techniques, such as by treating the substituted phenylhydrazine with any of the folIowing ~our types of reagents:
(a) an inner salt of a 3~ iminoalkylmer-capto)-l-propanesulfonic acid twhich may be prepared according to Reid and Schmidt, Ann. Chem. 676, 114 (1964) ~rom 1,3-propanesultone and a thioamide), to form an amidrazone followed by reaction with a source of phosgene, as by the following reaction sequence ~;~ (which is also illustrated in~Example 15~below), r ~ ~Z : ~20 ~ R2 CR3C-6--S03 ArNHNH2 ~ ArN~-ND~ --> ArNR-N~
E'cO~I ~ C~3; ~ 3 o HS~--503H amidr~zone oluen~ ~ ~U~ "Salt"
Ar-N N-H
13COCOCl ~ ..
:~Z~$~ 7 in which "Ar" is aro~atic as described below.
~b) An i~idate ester of the formula Cl~
RCC-oRd to form the corresponding amidrazone (as described, for instance, in the article by Neilson et al "The Chemistry of Amidrazones: Chem. Rev. 70, 151(1970j at ~ page 156), followed by reaction with a source of phos-; gene, as in (a) above, Rc and Rd being alkyl or other suitable radical.
(c) A compound of the formula , 3 C~3 RaO-c=N~ooRb or RaSC=NCOOR~
(where Ra and Rb are lower alkyl) in the presence of a base according to the following sequence:
l O
~C-NCOORb ~ ArNEN~2 - > ~Ar-N N-H
n~whl~h~R~ eJ de~lned~abovQ, e.q. methyl;
(d)~ A haloalkylnitrile (e.g. a fluoroalkyl, fluorochloroalkyl or fluorobromoalkyl nitrlle such as Cl~CF2CN, ~followed by reacti~on~with a sourc;e~ of phos-~
gene,~so that the reaction may proceed along ~the ;following~lines, for instance (and as als;o~illustrated 2~0 ~ in~Example 1~6 below), to form the aryl 3-haloalkyl r~aioli~- ~hus~
: ~ - , , : :
,. : ~ ~ - ~ . .- .: - :
~rNHNH2 ~ ClC~2CN ~ N-C-C~2Cl ~ --> A~-N~ N-~3 C~30H Cl~COCCl CF2 or COC12 In Examples 2 and 3 below the "Ar" portion of the aryl hydrazine (whose hydrazine portion is then modi-fied to form the triazoline ring) has halo substi-tuents at its 2 and 4 positions and an alkoxy group atits S position. Instead, in each of the processes illustrated above (and in the process of those Examples 2 and 3), the Ar group may be a phenyl ~; radical or a fluorophenyl ~e.g. Z-fluorophenyl) or a nitrophenyl (e.g. 3-nitrophenyl) alkoxyphenyl (e.g.
3-methoxyphenyl) or, most preferably, halonitrophenyl, - ~ particularly a fluoronitrophenyl (such as 2-fluoro-S-~- nitrophenyl) or haloalkoxyphenyl (such as 2-fluoro-5-alkoxyphenyl) and the aryl triazoline may then be treated to (a) alkylate the nitrogen at the 4-position of the triazoline ring (in known manner, e.g. with an alkyl or fluoroalkyl halide, such as with ClCHF2 to add the preferred - CHFz substituent) and (b) to introduce additional substituents onto the aro~atic 2Q r~ing, as by~halogenation wi~th chlorine or bromine (e.g. by reacting with C12~,~Brz~or SO2C12).
For instance the alkylation of the nitrogen at the
4-positlon may be effected first, after~which the nitro group (if present) may be reduced to an amino S~ ~group~in~conventional manner, the amino group may be converted~to a~hydroxyl group (as by conventional diazotization)~and then, preferabIy after etherifying the~OH~to form~an~alkoxy (e.g.~methoxy) group, the compound~;may~be haiogenated as above to place the~
30~ halogen substit~uent or substi~tuents on its benzene ring. The resulting compound may then be modified at the 5-position of the benzene ring to form the herbi-cidal compounds of this invention. For instance,, for making the preferred compounds of the invention in which the benzene ring has a 2-fluoro substituent, the starting material may be 2-fluoro-5-nitrophenylhydra-zine, which may be treated as described above to pro-duce successively a series of novel compounds such as 1-(2-fluoro-5-nitrophenyl)-4,5-dihydro-3-me~hyl-1,2,4-triazol-5(lH)-one, then 1-(2-fluoro-5-nitrophenyl-4,5-dihydro-4-difluoromethyl-3-methyl-1,2,4-triazol-5(1H)-one. These may be converted to the corresponding novel compounds having, at the 5-position of the benzene ring, successively - NH2, -OH and (prefer-ably) - OCH3, followed by halogenation to place, for instance, a chloro or bromo substituent at the 4-posi-tion of the benzene ring. Instead oE alkylating at ~-~ the 4-position of the ring triazdline at an early ;~, stage, e.g. prior to altering the nitro group, this alkylation step may be delayed until after the above-described halogenation of the ben7ene ring or even until after the conversion of thè alkoxy (or other) group at the 5-position of the benzene ring to one of the groups described at that position in Formulas I, II, III and IV (and Tables 2, 3, 4, and 5) above.
Similarly, when the reagent(s) used to react with the aryl hydrazine are such as to produce a triazolin-one having a haloalkyl (e.g. CHF2) group instead of an alkyl group on the carbon at the 3-position of the heterocyclic ring, t~he series of new compounds will includej successively, ~from 2-fluoro-5-nitrophenyl ; hydrazine) such compounds as 1-(2-fluoro-5-nitro-phenyl)-~,5-dihydro-3-difluoromethyl-1,2,4-triazol-5-(lH)-one, t~en 1-~2-fluoro-5-nitrophenyl)-4,5-dihydro-35~ 4-methyl ~or difluoromethyl)-3-difluoromethyl-1,2,4-.:j ~i :. ,~ .,., , ........... . :
;.: . .: . : ' ~' ,'.. : ' : .
triazol-5(lH)-one. These may be converted to the corresponding novel compounds having, at the 5-posi-tion o~ the benzene ring, succassively - NH2, -OH
and (preferably) -OCH3 followed by halogenation to place, for instance, a chloro or bromo substituent at the 4-position of the benzene ring. When the aryl hydrazine is 3-nitrophenyl hydrazine (instead of 2-fluoro-5-nitrophenylhydrazine) the series of nove].
compounds will include, successively, such compounds as 1-(3-nitrophenyl)-4,5-dihydro-3-di~luoromethyl-1,2,4-triazol-5(1H)-one, then 1-(3-nitrophenyl)-4,5-dihydro-4-methyl (or difluoromethyl)-3-difluoro-methyl-1,2,4-triazol-5(lH)-one. These may be con-verted ~o the corresponding novel compounds having, at the 3-position of the benzene ring, successively -NH2, -OH and (preferably) -OCH3, followed by halo-genation to place, for instance, chloro or bromo sub-stituents on the benzene ring.
Example 11 below illustrates a process for making a compound of this invention having a sulfonamide group at the 5-position of~the benzene ring by react-ing (a) a compound havlng an oxypropionic acid substi-tuent at that 5-position with (b) an aryl sulfonyliso-cyanate.
Another method for introducing the sulfo~amide group is by reacting (a) a compound having a phenolic OH group at that 5-position with (b) an N aryl (or .
alkyl etc.) sulfonylalkanoic acid amide having a reactive leaving~substituent (e.g. Br, Cl, mesylate or tosylate)~ on the alkane portion of the molecule, e.g.
CH3CHC-NHS02Ar.
Br : ~ . ~ : : : : :
:~2~&~
`~ Such a reaction can be carried out in the presence of a base (e.g. in acetone in the presence of sodium or potassium carbonate). This method is illustrated in Example 14 below.
The following Examples illustrate the preparation of the compounds of this invention.
Example 1 ; Ethyl [2,4-dichloro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-lH-l,Zs4-triazol-l-yl)phenoxy]acetate To a stirred mixture of 15.0 g (0.048 mole) of 1-(2,4-dichloro-5-hydroxyphenyl)-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one and 3.4 g (0.024 mole) of potassium carbonate in 100 mL of acetone was added 8.1 g (0.048 mole) of ethyl bromoacetate. The resultant mixture was stirred at reflux for three hours. After cooling, the mixture was evaporated under reduced pressure leaving a residue. This residue was partitioned between diethyl ether and water. The organic phase was washed with an aqueous 10% sodium hydroxide solution, then was dried over anhydrous magnesium sulfate and filtered. Evaporation of the filtrate under reduced pressure produced 17.8 g of a solid. A small porti~on of this solid was recrys-tallized Erom~methanol and water to yield ethyl [2,4-dichloro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-lH-1,2,4-triazol-1-yl)phenoxy]acetate (mp 118-119C), compound 17.
The nmr spectrum was consistent with the proposed structure.
The following compounds were also prepared by the process of~ Example l from~l (2,4-dichloro 5-hydroxy-phenyl)-4-difluoromethyl-4,5`-dihydro-3-methyl-1,2,4-triazol-5(1H)-one; 1-(4-chloro-2-fluoro-5-hydroxy-35~ pheny1)-4-diflu~oromethyl-4,5-dihydro-3-methyl-1,2,4-. ~
triazol-5(1H)-one; 2-[2,4-dichloro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-S-oxo-lH-1,2,4-triazol-1-yl)-phenoxy]propionic acid, compound Al; or 2-[4-chloro-2-fluoro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-lH-1,2,4-triazol-1-yl)phenoxy]propionic acid, compound A2, and one of the following:
Compound 14 methyl bromoacetate 17 ethyl bromoacetate 19 tert-butyl 2-bromopropionate 21 tert-butyl bromoacetat0 22 tert^butyl bromoacetate B6 1-methyl-2-propynyl 2-bromopropionate B7 1,1-dimethyl-2-propynyl 2-chloropropionate Bll bromoacetonitrile B16 ~-bromo-~-butyrolactone B22 chloromethyl methylether : 20 B23 chloromethyl methylsulfide Cl iodoacetamide ` C7 iodoacetamide C9 N-(l-methylpropyl) .~ 2-bromopropionami~e Example 2 . 2-[2-Chloro-4-fluoro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo~lH-1,2,4-triazol-. l-yl)phenoxy]propionic acid Step A 4-Chloro-2-fluoro~S-methoxyaniline from : 30 : 2-chloro-4~fluorophenol ~:
The intermedia~e 4-chloro-2-fluoro-5-methoxyaniline was prepared in a~:five step synthesis from commer-` cially available 2-chloro-4-fluorophenol as detailed ` ~ : by E. Nagano, et al. in European Patent Application ~69,855.
~, ~ . ... .. .
Step B 4-Chloro-2-fluoro-5-methoxyphenylhydrazine A stirred solution of 48.0 g (0.27 mole) of 4-chloro-2-fluoro-5-methoxyaniline in 500 mL of concentrated hydrochloric acid was cooled to -5C and 23.5 ~ (0.34 mole) of sodium nitrite in 100 mL of water was added dropwise. After complete addition the reaction mix-ture was stirred at 0C for one hour. A second solu-tion of 154.0 g (0.68 mole) of stannous chloride in 225 mL of concentrated hydrochloric acid was cooled to 0C, and the cold diazonium solution prepared above was added to it slowly. After complete addition the reaction mixture was allowed to warm to ambient temperature. The reaction mixture was filtered to collect a solid. This solid was dissolved in an -aqueous S0~ sodium hydroxide solution and the solution extracted with toluene. The toluene extract w~s dried with magnesium sulfate and filtered. The filtrate was concentrated under reduced pressure to yield 22.4 g of 4-chloro-2-fluoro-5-methoxyphenylhydrazine as a solid.
The nmr spectrum was consistent with the proposed structure.
~ Step C Pyruvic acid, 4-chloro-2-fluoro-5-methoxy-;~ ~ phenylhydrazone A stirred solution of 21.0 g (0.11 mole) of 4-chloro-25~ ~ Z-fluoro-5-methoxyphenylhydrazine and lOO mL of aqueous 10% ~hydrochloric acid in 100 mL of ethanol was ; warmed to 40C, and a solution o~ 10.0 g (O.llq mole) - ~ ' of pyruvic acid in 20 mL of water was added. Upon complete addition the reaction mixture was stirred for one hour. An additional 50 mL of~water was added and the reaction mixture ~iltered to collect a solid. The solid~was air dried to yield 29.0 g~oE pyruvic acid, ~: ~::: : : :
..
4-chloro-2-fluoro-5-methoxyphenylhydrazone; mp 166-169C.
The nmr spectrum was consistent with the proposed structure.
Step D l-t4-Chloro-2-fluoro-5-methoxyphenyl)-4,5-dihydro-3-methyl-1,2,4-triazol-5tlH)-one A stirred solution of 27.0 g (0.104 mole) of pyruvic acid, 4-chloro-2-fluoro-5-methoxyphenylhydrazone, 29.0 g (0.105 mole) of diphenyl phosphoryl azide, and 11.0 g (0.108 mole) of triethylamine in 500 mL of toluene was heated under reflux for four hours. The reaction mixture was cooled to ambient temperature and extracted with an aqueous 10% sodium hydroxide solu-tion. The extract was neutralized with gaseous carbon dioxide, and a solid was collected by filtration. The solid was air drie~ to yield 11.0 g of 1-(4-chloro-2-fluoro-5-methoxyphenyl)-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one; mp 193-195C.
The nmr spectrum was~ consistent with the proposed structure.
. :
Step E 1-(4-Chloro-2 f~1uoro-5-me~hoxyphenyl)-4,5-`~ ~ dihydro-4-difluoromethyl-3-methyl-1,2,4-triazol-5~1H)-one A stirred mixture of 10.0 g (0.039 mole) of 1-~4-chlpro-2-fluoro-5-methoxyphenyl)-4,5-dihydro-3-methyl-; ~ 1,2,4-triazol-5(lH)-one, 10.0 g ~0.031 mole) of~tetra-butylammonium bromide and 10.0 grams ~0.25 mole) of sodium hydroxide in 250 mL of cyclohexane was warmed ; to 60C. Chlorodifluoromethane (10.0 g, 0.12 mole) 30~ was bubbled into the reacti~on mixture. After complete " ~
~ addition the reaction mixture was warmed to reElux : ::: : :
- :~ , ;
: , .:: : : : . . . : .
where it stirred for one hour. The hot solution was decanted from a pot residue and cooled to ambient temperature. Methylene chloride was added to the cooled mixture to dissolve a solid precipitate. The mixture was washed with 10% hydrochloric acid then - with an aqueous 10~ sodium hydroxide solution. The organic layer was dried with anhydrous magnesium sulfate and filtered. The filtrate was concentrated under reduced pressure to yield S.0 g of 1-(4-chloro-2-~luoro-S-methoxyphenyl)-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-S(lH)-one; mp 86-88C.
The nmr spectrum wàs consistent with the proposed structure.
Step F 1-(4-Chloro-2-fluoro-5-hydroxyphenyl)-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazoI-5tlH)-one A stirred mixture of 4.6 g (0.015 mole) of 1-(4-chloro-2-fluoro-S-methoxyphenyl)-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-S(lH)-one in 200 mL of methylene chloride was cooled to 10C and a solution of 11.2 g (0.045) mole of boron tribromide in 45 mL of methylene chloride was added. Upon complete addition the reaction mixture was stirred~for four hours as it warmed to ambient temperature. A~ter this time 100 mL
of water was added, and stirring was continued for an additional 18 hours. The organic layer was separated, dried with anhydrous magnesium sulfate, and filtered.
The~filtrate~was concentrated under reduced pressure to yield 4.4 g of 1-(4-chloro-2-fluoro-5-hydroxy-30~ phenyl)-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one; mp 147-152C.
; The nmr spectrum was consistent with the proposed ; structure.
~.
.:~: ` :: ::
. .
: : ,, - ~ ,: :;: ~
..
~;$~i6~
Step G Methyl 2-[2~chloro-4-fluoro-5^(4-difluoro-methyl-4,5-dihydro-3-methyl-5-oxo-lH-1,2,4-~riazol-1-yl)phenoxy]propionate .
To a stirred mixture of 1.5 g (0.0051 mole) of 1-~4-chloro-2-fluoro 5-hydroxyphenyl)-4-difluoromethyl-4,5-dihydro-3~methyl-1,2,4-triazol-5(1H)-one and 0.12 g t0.0051 mole) o~ sodium hydride in 50 mL of N,N-di-methylEormamide was added 0.85 g (0.0051 mole) of methyl 2-bromopropionate. After complete addition the reaction mixture was heated at reflux for two hours, then cooled to room temperature and stirred for approximately 18 hours. The solvent was removed by evaporation under reduced pressure leaving a residue.
This residue was partitioned between diethyl ether and water. The organic phase was washed with an aqueous 10% sodium hydroxide solution. The organic phase was ; dried over anhydrous magnesium sulfate and filtered.
The filtrate was evaporated under reduced pressure to yield 1.5 g of methyl 2-[2-chloro-4-fluoro-5-(4-di-20~ fluoromethyl-4,5-dihydro-3-methyl-5-oxo-lH-1,2,4-tria-zol-l-yl)phenoxy]propionate as an oil, Compound 3.
The nmr spectrum was consistent with the proposed -~ ~ structure.
The following compounds were also prepared by the ~proce~ss of Example 2, Step~G, ~rom 1-(2,4-dichloro-5-hydroxyphenyl)-;4-difluoromethyl-4,5-dihydro-3 methyl`-1,2,4-triazol-5(1H)-one; 1-(4-chloro-2-fluoro-5-hydroxyphenyl)-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4~-tria~zol-5(1H)-one; or compound A2 and one o the 30 ~ ollowing~reagents~
Compound ~ ~ Reage~nt methyl ~romoacetate 2 ~ ~ methyl 2-bromopropionate ethyl 2~bromopropionate~
; 35 6 ethyl 2-bromopropionate 18 ethyl 4-bromo~ropionate ` e;thyl 2-bromoisobutyrate ; B21 N,N-diethyl-2-chloroacetamide C8 ~ ~ N,N-diethyl-2-chloroacetamide ~2S~7 Step H 2-[2-Chloro-4-fluoro-5-(4-difluoro~
methyl-4,5-dihydro-3-methyl-5-oxo-lH-1,2,4-triazol-1-yl)phenoxy]propionic acid A stirred mixture of 1.3 g ~0.0034 mole) of methyl 2-[2-chloro-4-fluoro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1~-l,Z,4-triazol-l-yl)phenoxy]pro-pionate and 1.0 g (0.018 mole) of potassium hydroxide in 15 mL of ethanol and 15 mL of water was heated at reflux for three hours. The mixture was allowed to cool to room temperature and stand for two days. The solvent was evaporated from the mixture leaving a solid. This solid was dissolved in water, and the solution was made acidic with concentrated hydro-chloric acid. This solution was extracted with methylene chloride. The extract was dried over anhy-drous magnesium sulfate and filtered. Evaporation of the solvent from the ~iltrate left 0.85 g of 2-[Z-- ~ chloro-4-fluoro-5-(4-difluoromethyl-4,5 dihydro-3-;~ methyl-S-oxo-lH-1,2,4-triazoI-l-yl)phenoxy]propionic-acid as a solid (mp 50-55~C),~ Compound AZ.
Compound Al was also prepared by the method of Example 2, Step H, from Compound 2.
Example 3 2-[4-Chloro-5-(4-difluoromethyl-4,5-dihydro-25~ ~ 3-methyl-S-oxo-lH-1~2,4-tria~ol-1-yl)-Z-methylphenoxy]propionlc~ acid Step A~ 4-Methyl-3-:ethoxyp~henylhydrazlne A~stirred mixture of~ 10~0.;0 ~g (0.73 mole3 of 4-methyl-3-methoxyanlline 1n~800 mL of concentrated hydrochlo-30~ ~; ric acid was cooled to ~5C. A solution of 501.5 g~
~2~ 7 (0.73 mole) of sodium nitrite in 250 mL of water was added slowly while maintaining the temperature of the reaction mixture below 0C. The resultant mixture was stirred at -5C for 30 minutes. A cold solu-tion of 330.0 ~ ~1.46 mole) of tin ~II) chloride dihydrate in 360 mL of concentrated hydrochloric acid was added over one hour. After complete addition the resultant mixture was allowed to warm to room temperature. A
solid precipitate formed and was collected by filtra-tion and stirred in 200 mL of water. This mixture was neutralized with 50% aqueous sodium hydroxide, and extracted with toluene. The extract was dried over anhydrous magnesium sulfate and filtered. The filtrate was evaporated under reduced pressure to yield 58.0 g of 4-methyl-3-methoxyphenylhydrazine as an oil.
The nmr spectrum was consistent with the pro-posed structure.
Step B Pyruvic acid, 4-methyl-3-methoxyphenyl-~ hydrazone ; ~ ~To a stirred mixture of 57.6 g (0.378 mole) of ~ ~ 4-methyl-3-methoxyphenylhydrazine in 400 mL of - ~ ~ ethanol and 400 mL of l~ hydrochloric acid was added 33.3~g (0.0378 mole) of pyruvic acid. Ater comple~e addition the mixture was stirred at room temperature for one hour,~and l liter of water was added.~ The mixture was extracted with methylene ~chloride. The extract was dried over anhydrous magnesium sulfate and filtered;~. The filtrate was evaporated under reduced pres~sure to yiel~d S9.0 g of pyruvic acid, 4-methyl-3-methoxyphenylhydrazone.
The nmr spectrum was consistent with the proposed structure.
, ~ - . - . . , :, . .............. .. .. ...
: . , . : . ~..... , -~6~6~7 Step C 4,5-Dihydro-1-(4-methyl-3-methoxyphenyl)-3-methyl-1,2,4-triazol-5(1H)-one To a stirred mixture of 56.8 g (0.26 mole) of pyruvic acid, 4-methyl-3-methoxyphenylhydrazone in 1500 mL of toluene was added 25.9 g (0.26 mole) of triethyl-amine. The mixture was heated at 50C, and 70.3 g (0.26 mole) of diphenyl phosphoryl azide was added.
The resultant mixture was heated at reflux for approximately lS hours; The mixture was cooled and extracted with four 200 mL portions of an aqueous 10%
sodium hydroxide solution. The aqueous extracts were combined, washed with toluene, and made acidic. The resultant solid was collected by filtration and air dried to yield 75.0 g of 4,5-dihydro-1-(4-methyl-3-methoxyphenyl)-3-methyl-1,2,4-triazol-5(1H)-one (mp 164-168C).
~- The nmr spectrum was consistent with the pro-posed structure.
; ~ ~ Step D 4-Difluoromethyl-4,5-dihydro-1-(4-methyl-3-methoxyphenyl)-3-methyl-1,2,4-triazol-StlH)-one ~ :
:
A stirred mixture of 60.0 g (0.28 mole) of 4,5-di-hydro-1-(4-methyl-3-methoxyphenyl)-3-methyl-1,~2,4-triazol-5(1H)-one, 60.0 g tO.l9 mole) ~o~ tetrabu~tyl-~ammonium bromide and 60.0 g~tl.5~mole) of powderedsodium~hydroxi~de in 2 liters~of~cyclohexane was heated at reflux. During a~two~hour period 60.0 g (0.67 mole~) of g~aseous difluorochloromethane was `bubbled into the~mixture. Afte~r complete~addition the~mixture was s~tirred at reflux~for~one hour, then ; al~lowed to cool to 70C. The supernatant liquid was d~eca~nted and~washed with aqueous 10% hydrochloric acid followed by an aqueous 10% sodium hydroxide solution. The organic layer was dried with magnesium sulfate and filtered. The filtrate was evaporated under reduced pressure to leave a solid. This solid was triturated with petroleum ether and filtered.
The filter cake was air dried to yield 18.5 g of 4-difluoromethyl-4,5-dihydro-1-(4-methyl-3-methoxy-phenyl)-3-methyl-1,2,4-triazol-5-(lH)-one.
The nmr spectrum was consistent with the proposed structure.
Step E 1-(2-Chloro-4-methyl-5-methoxyphenyl)-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(lH)-one ., .
A solution of 15.0 g (0.056 mole) of 4-difluoro-I5 methyl-4,5-dihydro-1-(4-methyl-3-methoxyphenyl)-3-methyl-1,2,4-triazol-5(1H)-one and 7.5 g (0.056 mole) of sulfuryl chloride in 100 mL of chloroform was ; stirred at room temperature for two hours. The reac-tion mixture was concentrated under reduced pressure to leave a residue. This residue was dissolved in methylene chloride and washed with an aqueous 10%
~; sodium hydroxide solution. The organic layer was `~ dr~ied with magnesium sulfate and filtered. The filtrate was concentrated under reduced pressure to yield 16.5 g of 1-(2-chloro-4-methyl-5-methoxy-phenyl)-4-difluoromethyl-4j5-dihydro-3-methyl-1,2,4-`~ triazol-5(1H)-one as a solid.
; The nmr spectrum was consis~tent with the proposed~structure.
30 Step F 1-(2-Chloro-4-methyl-5-hydroxyphenyl)-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(lH)-one . . . . .. .. . : . . . ..
. . ... . .
;6Ç~7 To a stirred solution oE 16.0 g (0.053 mole) of 1-(2-chloro-4-methyl-S-methoxyphenyl)-4-difluoro-methyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one - in 100 mL-of methylene chloride at 10C was added dropwise 39.6 g (0.16 mole) of boron tribromide. The resultant mixture was stirred at room temperature for two days. This mixture was washed with 100 mL of water. The organic layer was dried with anhydrous magnesium sulfate and filtered. The filtrate was concentrated under reducéd pressure to leave an oil.
This oil was stirred in petroleum ether:diethyl ether (90:10) forming a solid. The solid was collected by ~iltration to yield lO.S g of 1-(2-chloro-4-methyl-5-hydroxyphenyl)-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-S(lH)-one (mp 154-156C).
The nmr spectrum was consistent with the proposed structure.
Step G Methyl 2-[4-chloro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-S-oxo-lH-1,2,4-triazol-l-yl)-2-methylphenoxy]proplonate :.
In a manner similar to Example 2, Step G, the reac-tion of 3.0 g tO.Ol mole) of 1-(2-chloro-4-methyl-5-hydroxyphenyl)-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one, 0.25 g (0.01 mole) of sodium hydride and 1.75~g (0.01 mole) of methyl Z-bromopro-pionate in 100 mL of N,N-dimethylformamide produced ; 3.7 g of methyl 2-[4-chloro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5~-oxo-lH-1,2,4-triazol-1-yl)-2-methylphenoxy]propionate~as an oil~ Compound 4.
The nmr spectrum was consistent with the proposed~structure.
Compound 7 was prepared by the process described Or Compound 4, but using~ethyl 2-bromopropionate in ; Step G.
i , Step H 2-[4-Chloro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-lH-1,2,4-triazol-l-yl)-2-methylphenoxy]propionic acid In a manner similar to Example 2, Step H, the reac-tion of 3.3 g ~0.0088 mole) of methyl 2-~4-chloro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-lH-1,2,4-triazol-l-yl)-2-methylphenoxy]propionate with 1.5 g (0.27 mole) of potassium hydroxide in 50 mL of ethanol and 15 mL of water produced 2.7 g of 2-[4-chloro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-lH-1,2,4-triazol-1-yl)-2-methylphenoxy]propionic acid as a solid (mp 56-60C), Compound A3.
The nmr spectrum was consistent with the proposed structure, . ,~: ' Example 4 2-Nitropropyl 2-[2,4-dichloro-5-(4-difluoro-~;, methyl-4?5-dihydro-3-methyl-5-oxo-lH-I,2,4-~i ~ triazol-l-yi)phenoxy]propionate A stirred mixture of 0.5 g (0,0013 mole) of 2-[2,4-20 ~ dichloro-5-(4-difluoromethyl~-4,5-dihydro-3-methyl-5-~ oxo-lH-I,2,4-triazol-1-yl)phenoxy]propionic acid - ~ (Compound Al), 1.0 g (0.0095 mole) of 2-nitro-1-propanol and 0,05 g (0.0003 mol~e) of p-toIuenesul-fonic acid monohydrate in 60 mL of toluene was heated 25 ~ ~ at reflux. The water generated in the reaction was removed by col~lection in a De~an-Stark trap. After refluxlng for a totaI of two~hours, the solYent was r~emoYed by ~distillation unde~r~reduced pressure leav-;
ing~a residue,~ This residue was dissol~ed in diethyl 30~ ether and washed~first with~ water then witX an qLe ou s 1 0~ sodiur hydroxld~ ~olution, Tbe organic - 2$ -phase was dried over anhydrous magnesium sulfate and filtered. The filtrate was evaporated to yield 0.5 g of 2-nitropropyl 2-[Z,4-dichloro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-lH-1,2,4-triazol-1-yl)-phenoxy]propionate as an oil, Compound Bl.
The nmr spectrum was consistent with the proposed structure.
Compound 11 was also prepared by the method of Example 4 Erom Compound Al and n-butanol.
;
' Example_5 2-Propenyl 2-[2,4-dichloro-5-t4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-lH-1,2,4-triazol-1-yl)-phenoxy]propionate Under a dry nitrogen atmosphere, a :stirred solution of 0.5 g (0.0013 mole) of methyl 2-[2,4-dichloro-' ~; 5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-lH-' ' 1,2,4-triazol-1-yl)phenoxy]propionate (Compound 2) '~ and approximately 0.01 g o~ sodium methoxide in 30 mL of 2-propen-1-ol was heated at reflux. After ; 20 approximately 5 mL of methanol was collected in a ~' Dean-Stark trap, the reaction mixture was cooled ' ~ slightly, and the remaining solvent removed by distiilation under reduced pressure leaving a resi-due. This residue was dissolved in diethyl ether and ; 25 washed with~water. The organic phase was dried over anhydrous magnesium sulfate and~ fiItered. The fil-trate was evaporated under reduced pressure to yield 0.55 g of 2-propenyl 2-[2,4-dichloro-5-(4-difluoro-methyl-4,5-dihydro-3-methyl-5-oxo-lH-1,2,4-tria-zol-l-yl)phenox'y]propionat'e as an oil, Compound B2.
The nmr~spectrum was~consistent with the pro-poséd structurè.
~2i6~7 Analysis Calc'd for C16H15N3C12F2o4: C 45.52;H 3.58;N 9 95 Found: C 45.24;H 3.76;N 9.~7 The following compounds were also prepared by the process of Example 5 from 1-(2,4-dichloro-S-hydroxy-phenyl)-4-difluromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(lH)-one; compound Al; or compound A2 and the following reagents:
Compound Reagent 9 n-propanol 2-propanol n-propanol 16 2-propanol B3 2-propyn-1-ol B5 2-methoxyethanol Example 6 N-methylsulfonyl-2-[2,4-Dichloro-5-(4-difluoro-; methyl-4,5-dihydro-3-methyl-5-oxo-lH-1,2,4-; triazol-l-yl)phenoxy]propionamide 20 ~ Step A 2-[2,4-Dichloro-5-(4-difluromethyl-4,5-dihydro-3-methyl-5-oxo-lH-1,2,4-triazol-l-yl)phenoxy~-prDpionyl chloride ; A stirred mixture of 2.9 g (0.0075 mole) of 2-[2,4-di-chloro 5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-25~ lH-i,2,4-triazol-l-yl)phenoxy]propionic acid (Com-pound A-l) in 5 mL of thionyl chloride was heated at reflux for 1.5 hours. The mixture was cooled, and the excess~thionyl~chloride was~removed by evaporation undsr~reduced pressure, leaving~3.1 g of product as an ;30~ oil.~
Step~B ~ N-Methylsulfonyl-2-~[2,4-dichloro-5-(4-di-luoro-methyl-4,5~-dihydro-3-methyl-5-oxo-lH-1,Z,~4-trla,ol-1-yl)phenoxy]propioDamide ~, , - : ..
A mixture of 0.56 g of the oil from Step A and 0.56 g (0.0059 ~ole) of methanesulfonamide was heated at 80~C
for 3.5 hours. The mixture was cooled and diluted - with water, forming a gummy precipitate. The water was decanted, and the residue was partitioned between water and methylene chloride. The organic phase was washed with three 100 ml portions of water, dried over anhydrous magnesium sulfate, and filtered. The ~
trate was evaporated under reduced pressure to leave a tan solid which was dissolved in 30 mL of 1~ sodium hydroxide and 50 mL of water. The basic mixture was filtered, and the filtrate was made acidic with con-centrated hydrochloric acid. A precipitate formed and was collected by Eiltration. The filter cake was washed with water and dried to yield 0.34 g of N-meth-~-~ ylsulfonyl-2-[2,4-dichloro-5-(4-difluoromethyl-4,5-di-hydro-3-methyl-5-oxo-lH-1,2,4-triazol-1-yl)phenoxy]pro-pionamide (mp 185-188C), Compound C3.
The nmr spectrum was consistent with the proposed structure.
-~ Analysis Calc'd for C14HI4C12F2N405S: C 36.61; H 3.07; N 12.20 Found: C 36.79; H 3.01; N 12.41 Compounds C4, C5 and C6 were prepared by the pro-cess described in Example 6 usin~ trifluoromethanesul-fonamide, ammonia and methylamine respectively in Step B. Compounds C2 and C18 were prepared by the method of Example 6 from Compound A2, using methylamine and methanesulfonamide respectively in Step B.
~ ~ Example 7 ; Ethyl 2-[2,4-dibromo-5-(4-difluoromethyl-4,5-; dihydro-3-methyl-S-oxo-lH-1,2,4-triazol-1-ylj-phenoxy]propionate Step A 1-(2,4-Dibromo-5-methoxyphenyl)-4-difluoro-methyl-4,5-dihydro-3-methyl-1,2,4-triazol-
30~ halogen substit~uent or substi~tuents on its benzene ring. The resulting compound may then be modified at the 5-position of the benzene ring to form the herbi-cidal compounds of this invention. For instance,, for making the preferred compounds of the invention in which the benzene ring has a 2-fluoro substituent, the starting material may be 2-fluoro-5-nitrophenylhydra-zine, which may be treated as described above to pro-duce successively a series of novel compounds such as 1-(2-fluoro-5-nitrophenyl)-4,5-dihydro-3-me~hyl-1,2,4-triazol-5(lH)-one, then 1-(2-fluoro-5-nitrophenyl-4,5-dihydro-4-difluoromethyl-3-methyl-1,2,4-triazol-5(1H)-one. These may be converted to the corresponding novel compounds having, at the 5-position of the benzene ring, successively - NH2, -OH and (prefer-ably) - OCH3, followed by halogenation to place, for instance, a chloro or bromo substituent at the 4-posi-tion of the benzene ring. Instead oE alkylating at ~-~ the 4-position of the ring triazdline at an early ;~, stage, e.g. prior to altering the nitro group, this alkylation step may be delayed until after the above-described halogenation of the ben7ene ring or even until after the conversion of thè alkoxy (or other) group at the 5-position of the benzene ring to one of the groups described at that position in Formulas I, II, III and IV (and Tables 2, 3, 4, and 5) above.
Similarly, when the reagent(s) used to react with the aryl hydrazine are such as to produce a triazolin-one having a haloalkyl (e.g. CHF2) group instead of an alkyl group on the carbon at the 3-position of the heterocyclic ring, t~he series of new compounds will includej successively, ~from 2-fluoro-5-nitrophenyl ; hydrazine) such compounds as 1-(2-fluoro-5-nitro-phenyl)-~,5-dihydro-3-difluoromethyl-1,2,4-triazol-5-(lH)-one, t~en 1-~2-fluoro-5-nitrophenyl)-4,5-dihydro-35~ 4-methyl ~or difluoromethyl)-3-difluoromethyl-1,2,4-.:j ~i :. ,~ .,., , ........... . :
;.: . .: . : ' ~' ,'.. : ' : .
triazol-5(lH)-one. These may be converted to the corresponding novel compounds having, at the 5-posi-tion o~ the benzene ring, succassively - NH2, -OH
and (preferably) -OCH3 followed by halogenation to place, for instance, a chloro or bromo substituent at the 4-position of the benzene ring. When the aryl hydrazine is 3-nitrophenyl hydrazine (instead of 2-fluoro-5-nitrophenylhydrazine) the series of nove].
compounds will include, successively, such compounds as 1-(3-nitrophenyl)-4,5-dihydro-3-di~luoromethyl-1,2,4-triazol-5(1H)-one, then 1-(3-nitrophenyl)-4,5-dihydro-4-methyl (or difluoromethyl)-3-difluoro-methyl-1,2,4-triazol-5(lH)-one. These may be con-verted ~o the corresponding novel compounds having, at the 3-position of the benzene ring, successively -NH2, -OH and (preferably) -OCH3, followed by halo-genation to place, for instance, chloro or bromo sub-stituents on the benzene ring.
Example 11 below illustrates a process for making a compound of this invention having a sulfonamide group at the 5-position of~the benzene ring by react-ing (a) a compound havlng an oxypropionic acid substi-tuent at that 5-position with (b) an aryl sulfonyliso-cyanate.
Another method for introducing the sulfo~amide group is by reacting (a) a compound having a phenolic OH group at that 5-position with (b) an N aryl (or .
alkyl etc.) sulfonylalkanoic acid amide having a reactive leaving~substituent (e.g. Br, Cl, mesylate or tosylate)~ on the alkane portion of the molecule, e.g.
CH3CHC-NHS02Ar.
Br : ~ . ~ : : : : :
:~2~&~
`~ Such a reaction can be carried out in the presence of a base (e.g. in acetone in the presence of sodium or potassium carbonate). This method is illustrated in Example 14 below.
The following Examples illustrate the preparation of the compounds of this invention.
Example 1 ; Ethyl [2,4-dichloro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-lH-l,Zs4-triazol-l-yl)phenoxy]acetate To a stirred mixture of 15.0 g (0.048 mole) of 1-(2,4-dichloro-5-hydroxyphenyl)-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one and 3.4 g (0.024 mole) of potassium carbonate in 100 mL of acetone was added 8.1 g (0.048 mole) of ethyl bromoacetate. The resultant mixture was stirred at reflux for three hours. After cooling, the mixture was evaporated under reduced pressure leaving a residue. This residue was partitioned between diethyl ether and water. The organic phase was washed with an aqueous 10% sodium hydroxide solution, then was dried over anhydrous magnesium sulfate and filtered. Evaporation of the filtrate under reduced pressure produced 17.8 g of a solid. A small porti~on of this solid was recrys-tallized Erom~methanol and water to yield ethyl [2,4-dichloro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-lH-1,2,4-triazol-1-yl)phenoxy]acetate (mp 118-119C), compound 17.
The nmr spectrum was consistent with the proposed structure.
The following compounds were also prepared by the process of~ Example l from~l (2,4-dichloro 5-hydroxy-phenyl)-4-difluoromethyl-4,5`-dihydro-3-methyl-1,2,4-triazol-5(1H)-one; 1-(4-chloro-2-fluoro-5-hydroxy-35~ pheny1)-4-diflu~oromethyl-4,5-dihydro-3-methyl-1,2,4-. ~
triazol-5(1H)-one; 2-[2,4-dichloro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-S-oxo-lH-1,2,4-triazol-1-yl)-phenoxy]propionic acid, compound Al; or 2-[4-chloro-2-fluoro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-lH-1,2,4-triazol-1-yl)phenoxy]propionic acid, compound A2, and one of the following:
Compound 14 methyl bromoacetate 17 ethyl bromoacetate 19 tert-butyl 2-bromopropionate 21 tert-butyl bromoacetat0 22 tert^butyl bromoacetate B6 1-methyl-2-propynyl 2-bromopropionate B7 1,1-dimethyl-2-propynyl 2-chloropropionate Bll bromoacetonitrile B16 ~-bromo-~-butyrolactone B22 chloromethyl methylether : 20 B23 chloromethyl methylsulfide Cl iodoacetamide ` C7 iodoacetamide C9 N-(l-methylpropyl) .~ 2-bromopropionami~e Example 2 . 2-[2-Chloro-4-fluoro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo~lH-1,2,4-triazol-. l-yl)phenoxy]propionic acid Step A 4-Chloro-2-fluoro~S-methoxyaniline from : 30 : 2-chloro-4~fluorophenol ~:
The intermedia~e 4-chloro-2-fluoro-5-methoxyaniline was prepared in a~:five step synthesis from commer-` cially available 2-chloro-4-fluorophenol as detailed ` ~ : by E. Nagano, et al. in European Patent Application ~69,855.
~, ~ . ... .. .
Step B 4-Chloro-2-fluoro-5-methoxyphenylhydrazine A stirred solution of 48.0 g (0.27 mole) of 4-chloro-2-fluoro-5-methoxyaniline in 500 mL of concentrated hydrochloric acid was cooled to -5C and 23.5 ~ (0.34 mole) of sodium nitrite in 100 mL of water was added dropwise. After complete addition the reaction mix-ture was stirred at 0C for one hour. A second solu-tion of 154.0 g (0.68 mole) of stannous chloride in 225 mL of concentrated hydrochloric acid was cooled to 0C, and the cold diazonium solution prepared above was added to it slowly. After complete addition the reaction mixture was allowed to warm to ambient temperature. The reaction mixture was filtered to collect a solid. This solid was dissolved in an -aqueous S0~ sodium hydroxide solution and the solution extracted with toluene. The toluene extract w~s dried with magnesium sulfate and filtered. The filtrate was concentrated under reduced pressure to yield 22.4 g of 4-chloro-2-fluoro-5-methoxyphenylhydrazine as a solid.
The nmr spectrum was consistent with the proposed structure.
~ Step C Pyruvic acid, 4-chloro-2-fluoro-5-methoxy-;~ ~ phenylhydrazone A stirred solution of 21.0 g (0.11 mole) of 4-chloro-25~ ~ Z-fluoro-5-methoxyphenylhydrazine and lOO mL of aqueous 10% ~hydrochloric acid in 100 mL of ethanol was ; warmed to 40C, and a solution o~ 10.0 g (O.llq mole) - ~ ' of pyruvic acid in 20 mL of water was added. Upon complete addition the reaction mixture was stirred for one hour. An additional 50 mL of~water was added and the reaction mixture ~iltered to collect a solid. The solid~was air dried to yield 29.0 g~oE pyruvic acid, ~: ~::: : : :
..
4-chloro-2-fluoro-5-methoxyphenylhydrazone; mp 166-169C.
The nmr spectrum was consistent with the proposed structure.
Step D l-t4-Chloro-2-fluoro-5-methoxyphenyl)-4,5-dihydro-3-methyl-1,2,4-triazol-5tlH)-one A stirred solution of 27.0 g (0.104 mole) of pyruvic acid, 4-chloro-2-fluoro-5-methoxyphenylhydrazone, 29.0 g (0.105 mole) of diphenyl phosphoryl azide, and 11.0 g (0.108 mole) of triethylamine in 500 mL of toluene was heated under reflux for four hours. The reaction mixture was cooled to ambient temperature and extracted with an aqueous 10% sodium hydroxide solu-tion. The extract was neutralized with gaseous carbon dioxide, and a solid was collected by filtration. The solid was air drie~ to yield 11.0 g of 1-(4-chloro-2-fluoro-5-methoxyphenyl)-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one; mp 193-195C.
The nmr spectrum was~ consistent with the proposed structure.
. :
Step E 1-(4-Chloro-2 f~1uoro-5-me~hoxyphenyl)-4,5-`~ ~ dihydro-4-difluoromethyl-3-methyl-1,2,4-triazol-5~1H)-one A stirred mixture of 10.0 g (0.039 mole) of 1-~4-chlpro-2-fluoro-5-methoxyphenyl)-4,5-dihydro-3-methyl-; ~ 1,2,4-triazol-5(lH)-one, 10.0 g ~0.031 mole) of~tetra-butylammonium bromide and 10.0 grams ~0.25 mole) of sodium hydroxide in 250 mL of cyclohexane was warmed ; to 60C. Chlorodifluoromethane (10.0 g, 0.12 mole) 30~ was bubbled into the reacti~on mixture. After complete " ~
~ addition the reaction mixture was warmed to reElux : ::: : :
- :~ , ;
: , .:: : : : . . . : .
where it stirred for one hour. The hot solution was decanted from a pot residue and cooled to ambient temperature. Methylene chloride was added to the cooled mixture to dissolve a solid precipitate. The mixture was washed with 10% hydrochloric acid then - with an aqueous 10~ sodium hydroxide solution. The organic layer was dried with anhydrous magnesium sulfate and filtered. The filtrate was concentrated under reduced pressure to yield S.0 g of 1-(4-chloro-2-~luoro-S-methoxyphenyl)-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-S(lH)-one; mp 86-88C.
The nmr spectrum wàs consistent with the proposed structure.
Step F 1-(4-Chloro-2-fluoro-5-hydroxyphenyl)-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazoI-5tlH)-one A stirred mixture of 4.6 g (0.015 mole) of 1-(4-chloro-2-fluoro-S-methoxyphenyl)-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-S(lH)-one in 200 mL of methylene chloride was cooled to 10C and a solution of 11.2 g (0.045) mole of boron tribromide in 45 mL of methylene chloride was added. Upon complete addition the reaction mixture was stirred~for four hours as it warmed to ambient temperature. A~ter this time 100 mL
of water was added, and stirring was continued for an additional 18 hours. The organic layer was separated, dried with anhydrous magnesium sulfate, and filtered.
The~filtrate~was concentrated under reduced pressure to yield 4.4 g of 1-(4-chloro-2-fluoro-5-hydroxy-30~ phenyl)-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one; mp 147-152C.
; The nmr spectrum was consistent with the proposed ; structure.
~.
.:~: ` :: ::
. .
: : ,, - ~ ,: :;: ~
..
~;$~i6~
Step G Methyl 2-[2~chloro-4-fluoro-5^(4-difluoro-methyl-4,5-dihydro-3-methyl-5-oxo-lH-1,2,4-~riazol-1-yl)phenoxy]propionate .
To a stirred mixture of 1.5 g (0.0051 mole) of 1-~4-chloro-2-fluoro 5-hydroxyphenyl)-4-difluoromethyl-4,5-dihydro-3~methyl-1,2,4-triazol-5(1H)-one and 0.12 g t0.0051 mole) o~ sodium hydride in 50 mL of N,N-di-methylEormamide was added 0.85 g (0.0051 mole) of methyl 2-bromopropionate. After complete addition the reaction mixture was heated at reflux for two hours, then cooled to room temperature and stirred for approximately 18 hours. The solvent was removed by evaporation under reduced pressure leaving a residue.
This residue was partitioned between diethyl ether and water. The organic phase was washed with an aqueous 10% sodium hydroxide solution. The organic phase was ; dried over anhydrous magnesium sulfate and filtered.
The filtrate was evaporated under reduced pressure to yield 1.5 g of methyl 2-[2-chloro-4-fluoro-5-(4-di-20~ fluoromethyl-4,5-dihydro-3-methyl-5-oxo-lH-1,2,4-tria-zol-l-yl)phenoxy]propionate as an oil, Compound 3.
The nmr spectrum was consistent with the proposed -~ ~ structure.
The following compounds were also prepared by the ~proce~ss of Example 2, Step~G, ~rom 1-(2,4-dichloro-5-hydroxyphenyl)-;4-difluoromethyl-4,5-dihydro-3 methyl`-1,2,4-triazol-5(1H)-one; 1-(4-chloro-2-fluoro-5-hydroxyphenyl)-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4~-tria~zol-5(1H)-one; or compound A2 and one o the 30 ~ ollowing~reagents~
Compound ~ ~ Reage~nt methyl ~romoacetate 2 ~ ~ methyl 2-bromopropionate ethyl 2~bromopropionate~
; 35 6 ethyl 2-bromopropionate 18 ethyl 4-bromo~ropionate ` e;thyl 2-bromoisobutyrate ; B21 N,N-diethyl-2-chloroacetamide C8 ~ ~ N,N-diethyl-2-chloroacetamide ~2S~7 Step H 2-[2-Chloro-4-fluoro-5-(4-difluoro~
methyl-4,5-dihydro-3-methyl-5-oxo-lH-1,2,4-triazol-1-yl)phenoxy]propionic acid A stirred mixture of 1.3 g ~0.0034 mole) of methyl 2-[2-chloro-4-fluoro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1~-l,Z,4-triazol-l-yl)phenoxy]pro-pionate and 1.0 g (0.018 mole) of potassium hydroxide in 15 mL of ethanol and 15 mL of water was heated at reflux for three hours. The mixture was allowed to cool to room temperature and stand for two days. The solvent was evaporated from the mixture leaving a solid. This solid was dissolved in water, and the solution was made acidic with concentrated hydro-chloric acid. This solution was extracted with methylene chloride. The extract was dried over anhy-drous magnesium sulfate and filtered. Evaporation of the solvent from the ~iltrate left 0.85 g of 2-[Z-- ~ chloro-4-fluoro-5-(4-difluoromethyl-4,5 dihydro-3-;~ methyl-S-oxo-lH-1,2,4-triazoI-l-yl)phenoxy]propionic-acid as a solid (mp 50-55~C),~ Compound AZ.
Compound Al was also prepared by the method of Example 2, Step H, from Compound 2.
Example 3 2-[4-Chloro-5-(4-difluoromethyl-4,5-dihydro-25~ ~ 3-methyl-S-oxo-lH-1~2,4-tria~ol-1-yl)-Z-methylphenoxy]propionlc~ acid Step A~ 4-Methyl-3-:ethoxyp~henylhydrazlne A~stirred mixture of~ 10~0.;0 ~g (0.73 mole3 of 4-methyl-3-methoxyanlline 1n~800 mL of concentrated hydrochlo-30~ ~; ric acid was cooled to ~5C. A solution of 501.5 g~
~2~ 7 (0.73 mole) of sodium nitrite in 250 mL of water was added slowly while maintaining the temperature of the reaction mixture below 0C. The resultant mixture was stirred at -5C for 30 minutes. A cold solu-tion of 330.0 ~ ~1.46 mole) of tin ~II) chloride dihydrate in 360 mL of concentrated hydrochloric acid was added over one hour. After complete addition the resultant mixture was allowed to warm to room temperature. A
solid precipitate formed and was collected by filtra-tion and stirred in 200 mL of water. This mixture was neutralized with 50% aqueous sodium hydroxide, and extracted with toluene. The extract was dried over anhydrous magnesium sulfate and filtered. The filtrate was evaporated under reduced pressure to yield 58.0 g of 4-methyl-3-methoxyphenylhydrazine as an oil.
The nmr spectrum was consistent with the pro-posed structure.
Step B Pyruvic acid, 4-methyl-3-methoxyphenyl-~ hydrazone ; ~ ~To a stirred mixture of 57.6 g (0.378 mole) of ~ ~ 4-methyl-3-methoxyphenylhydrazine in 400 mL of - ~ ~ ethanol and 400 mL of l~ hydrochloric acid was added 33.3~g (0.0378 mole) of pyruvic acid. Ater comple~e addition the mixture was stirred at room temperature for one hour,~and l liter of water was added.~ The mixture was extracted with methylene ~chloride. The extract was dried over anhydrous magnesium sulfate and filtered;~. The filtrate was evaporated under reduced pres~sure to yiel~d S9.0 g of pyruvic acid, 4-methyl-3-methoxyphenylhydrazone.
The nmr spectrum was consistent with the proposed structure.
, ~ - . - . . , :, . .............. .. .. ...
: . , . : . ~..... , -~6~6~7 Step C 4,5-Dihydro-1-(4-methyl-3-methoxyphenyl)-3-methyl-1,2,4-triazol-5(1H)-one To a stirred mixture of 56.8 g (0.26 mole) of pyruvic acid, 4-methyl-3-methoxyphenylhydrazone in 1500 mL of toluene was added 25.9 g (0.26 mole) of triethyl-amine. The mixture was heated at 50C, and 70.3 g (0.26 mole) of diphenyl phosphoryl azide was added.
The resultant mixture was heated at reflux for approximately lS hours; The mixture was cooled and extracted with four 200 mL portions of an aqueous 10%
sodium hydroxide solution. The aqueous extracts were combined, washed with toluene, and made acidic. The resultant solid was collected by filtration and air dried to yield 75.0 g of 4,5-dihydro-1-(4-methyl-3-methoxyphenyl)-3-methyl-1,2,4-triazol-5(1H)-one (mp 164-168C).
~- The nmr spectrum was consistent with the pro-posed structure.
; ~ ~ Step D 4-Difluoromethyl-4,5-dihydro-1-(4-methyl-3-methoxyphenyl)-3-methyl-1,2,4-triazol-StlH)-one ~ :
:
A stirred mixture of 60.0 g (0.28 mole) of 4,5-di-hydro-1-(4-methyl-3-methoxyphenyl)-3-methyl-1,~2,4-triazol-5(1H)-one, 60.0 g tO.l9 mole) ~o~ tetrabu~tyl-~ammonium bromide and 60.0 g~tl.5~mole) of powderedsodium~hydroxi~de in 2 liters~of~cyclohexane was heated at reflux. During a~two~hour period 60.0 g (0.67 mole~) of g~aseous difluorochloromethane was `bubbled into the~mixture. Afte~r complete~addition the~mixture was s~tirred at reflux~for~one hour, then ; al~lowed to cool to 70C. The supernatant liquid was d~eca~nted and~washed with aqueous 10% hydrochloric acid followed by an aqueous 10% sodium hydroxide solution. The organic layer was dried with magnesium sulfate and filtered. The filtrate was evaporated under reduced pressure to leave a solid. This solid was triturated with petroleum ether and filtered.
The filter cake was air dried to yield 18.5 g of 4-difluoromethyl-4,5-dihydro-1-(4-methyl-3-methoxy-phenyl)-3-methyl-1,2,4-triazol-5-(lH)-one.
The nmr spectrum was consistent with the proposed structure.
Step E 1-(2-Chloro-4-methyl-5-methoxyphenyl)-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(lH)-one ., .
A solution of 15.0 g (0.056 mole) of 4-difluoro-I5 methyl-4,5-dihydro-1-(4-methyl-3-methoxyphenyl)-3-methyl-1,2,4-triazol-5(1H)-one and 7.5 g (0.056 mole) of sulfuryl chloride in 100 mL of chloroform was ; stirred at room temperature for two hours. The reac-tion mixture was concentrated under reduced pressure to leave a residue. This residue was dissolved in methylene chloride and washed with an aqueous 10%
~; sodium hydroxide solution. The organic layer was `~ dr~ied with magnesium sulfate and filtered. The filtrate was concentrated under reduced pressure to yield 16.5 g of 1-(2-chloro-4-methyl-5-methoxy-phenyl)-4-difluoromethyl-4j5-dihydro-3-methyl-1,2,4-`~ triazol-5(1H)-one as a solid.
; The nmr spectrum was consis~tent with the proposed~structure.
30 Step F 1-(2-Chloro-4-methyl-5-hydroxyphenyl)-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(lH)-one . . . . .. .. . : . . . ..
. . ... . .
;6Ç~7 To a stirred solution oE 16.0 g (0.053 mole) of 1-(2-chloro-4-methyl-S-methoxyphenyl)-4-difluoro-methyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one - in 100 mL-of methylene chloride at 10C was added dropwise 39.6 g (0.16 mole) of boron tribromide. The resultant mixture was stirred at room temperature for two days. This mixture was washed with 100 mL of water. The organic layer was dried with anhydrous magnesium sulfate and filtered. The filtrate was concentrated under reducéd pressure to leave an oil.
This oil was stirred in petroleum ether:diethyl ether (90:10) forming a solid. The solid was collected by ~iltration to yield lO.S g of 1-(2-chloro-4-methyl-5-hydroxyphenyl)-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-S(lH)-one (mp 154-156C).
The nmr spectrum was consistent with the proposed structure.
Step G Methyl 2-[4-chloro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-S-oxo-lH-1,2,4-triazol-l-yl)-2-methylphenoxy]proplonate :.
In a manner similar to Example 2, Step G, the reac-tion of 3.0 g tO.Ol mole) of 1-(2-chloro-4-methyl-5-hydroxyphenyl)-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one, 0.25 g (0.01 mole) of sodium hydride and 1.75~g (0.01 mole) of methyl Z-bromopro-pionate in 100 mL of N,N-dimethylformamide produced ; 3.7 g of methyl 2-[4-chloro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5~-oxo-lH-1,2,4-triazol-1-yl)-2-methylphenoxy]propionate~as an oil~ Compound 4.
The nmr spectrum was consistent with the proposed~structure.
Compound 7 was prepared by the process described Or Compound 4, but using~ethyl 2-bromopropionate in ; Step G.
i , Step H 2-[4-Chloro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-lH-1,2,4-triazol-l-yl)-2-methylphenoxy]propionic acid In a manner similar to Example 2, Step H, the reac-tion of 3.3 g ~0.0088 mole) of methyl 2-~4-chloro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-lH-1,2,4-triazol-l-yl)-2-methylphenoxy]propionate with 1.5 g (0.27 mole) of potassium hydroxide in 50 mL of ethanol and 15 mL of water produced 2.7 g of 2-[4-chloro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-lH-1,2,4-triazol-1-yl)-2-methylphenoxy]propionic acid as a solid (mp 56-60C), Compound A3.
The nmr spectrum was consistent with the proposed structure, . ,~: ' Example 4 2-Nitropropyl 2-[2,4-dichloro-5-(4-difluoro-~;, methyl-4?5-dihydro-3-methyl-5-oxo-lH-I,2,4-~i ~ triazol-l-yi)phenoxy]propionate A stirred mixture of 0.5 g (0,0013 mole) of 2-[2,4-20 ~ dichloro-5-(4-difluoromethyl~-4,5-dihydro-3-methyl-5-~ oxo-lH-I,2,4-triazol-1-yl)phenoxy]propionic acid - ~ (Compound Al), 1.0 g (0.0095 mole) of 2-nitro-1-propanol and 0,05 g (0.0003 mol~e) of p-toIuenesul-fonic acid monohydrate in 60 mL of toluene was heated 25 ~ ~ at reflux. The water generated in the reaction was removed by col~lection in a De~an-Stark trap. After refluxlng for a totaI of two~hours, the solYent was r~emoYed by ~distillation unde~r~reduced pressure leav-;
ing~a residue,~ This residue was dissol~ed in diethyl 30~ ether and washed~first with~ water then witX an qLe ou s 1 0~ sodiur hydroxld~ ~olution, Tbe organic - 2$ -phase was dried over anhydrous magnesium sulfate and filtered. The filtrate was evaporated to yield 0.5 g of 2-nitropropyl 2-[Z,4-dichloro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-lH-1,2,4-triazol-1-yl)-phenoxy]propionate as an oil, Compound Bl.
The nmr spectrum was consistent with the proposed structure.
Compound 11 was also prepared by the method of Example 4 Erom Compound Al and n-butanol.
;
' Example_5 2-Propenyl 2-[2,4-dichloro-5-t4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-lH-1,2,4-triazol-1-yl)-phenoxy]propionate Under a dry nitrogen atmosphere, a :stirred solution of 0.5 g (0.0013 mole) of methyl 2-[2,4-dichloro-' ~; 5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-lH-' ' 1,2,4-triazol-1-yl)phenoxy]propionate (Compound 2) '~ and approximately 0.01 g o~ sodium methoxide in 30 mL of 2-propen-1-ol was heated at reflux. After ; 20 approximately 5 mL of methanol was collected in a ~' Dean-Stark trap, the reaction mixture was cooled ' ~ slightly, and the remaining solvent removed by distiilation under reduced pressure leaving a resi-due. This residue was dissolved in diethyl ether and ; 25 washed with~water. The organic phase was dried over anhydrous magnesium sulfate and~ fiItered. The fil-trate was evaporated under reduced pressure to yield 0.55 g of 2-propenyl 2-[2,4-dichloro-5-(4-difluoro-methyl-4,5-dihydro-3-methyl-5-oxo-lH-1,2,4-tria-zol-l-yl)phenox'y]propionat'e as an oil, Compound B2.
The nmr~spectrum was~consistent with the pro-poséd structurè.
~2i6~7 Analysis Calc'd for C16H15N3C12F2o4: C 45.52;H 3.58;N 9 95 Found: C 45.24;H 3.76;N 9.~7 The following compounds were also prepared by the process of Example 5 from 1-(2,4-dichloro-S-hydroxy-phenyl)-4-difluromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(lH)-one; compound Al; or compound A2 and the following reagents:
Compound Reagent 9 n-propanol 2-propanol n-propanol 16 2-propanol B3 2-propyn-1-ol B5 2-methoxyethanol Example 6 N-methylsulfonyl-2-[2,4-Dichloro-5-(4-difluoro-; methyl-4,5-dihydro-3-methyl-5-oxo-lH-1,2,4-; triazol-l-yl)phenoxy]propionamide 20 ~ Step A 2-[2,4-Dichloro-5-(4-difluromethyl-4,5-dihydro-3-methyl-5-oxo-lH-1,2,4-triazol-l-yl)phenoxy~-prDpionyl chloride ; A stirred mixture of 2.9 g (0.0075 mole) of 2-[2,4-di-chloro 5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-25~ lH-i,2,4-triazol-l-yl)phenoxy]propionic acid (Com-pound A-l) in 5 mL of thionyl chloride was heated at reflux for 1.5 hours. The mixture was cooled, and the excess~thionyl~chloride was~removed by evaporation undsr~reduced pressure, leaving~3.1 g of product as an ;30~ oil.~
Step~B ~ N-Methylsulfonyl-2-~[2,4-dichloro-5-(4-di-luoro-methyl-4,5~-dihydro-3-methyl-5-oxo-lH-1,Z,~4-trla,ol-1-yl)phenoxy]propioDamide ~, , - : ..
A mixture of 0.56 g of the oil from Step A and 0.56 g (0.0059 ~ole) of methanesulfonamide was heated at 80~C
for 3.5 hours. The mixture was cooled and diluted - with water, forming a gummy precipitate. The water was decanted, and the residue was partitioned between water and methylene chloride. The organic phase was washed with three 100 ml portions of water, dried over anhydrous magnesium sulfate, and filtered. The ~
trate was evaporated under reduced pressure to leave a tan solid which was dissolved in 30 mL of 1~ sodium hydroxide and 50 mL of water. The basic mixture was filtered, and the filtrate was made acidic with con-centrated hydrochloric acid. A precipitate formed and was collected by Eiltration. The filter cake was washed with water and dried to yield 0.34 g of N-meth-~-~ ylsulfonyl-2-[2,4-dichloro-5-(4-difluoromethyl-4,5-di-hydro-3-methyl-5-oxo-lH-1,2,4-triazol-1-yl)phenoxy]pro-pionamide (mp 185-188C), Compound C3.
The nmr spectrum was consistent with the proposed structure.
-~ Analysis Calc'd for C14HI4C12F2N405S: C 36.61; H 3.07; N 12.20 Found: C 36.79; H 3.01; N 12.41 Compounds C4, C5 and C6 were prepared by the pro-cess described in Example 6 usin~ trifluoromethanesul-fonamide, ammonia and methylamine respectively in Step B. Compounds C2 and C18 were prepared by the method of Example 6 from Compound A2, using methylamine and methanesulfonamide respectively in Step B.
~ ~ Example 7 ; Ethyl 2-[2,4-dibromo-5-(4-difluoromethyl-4,5-; dihydro-3-methyl-S-oxo-lH-1,2,4-triazol-1-ylj-phenoxy]propionate Step A 1-(2,4-Dibromo-5-methoxyphenyl)-4-difluoro-methyl-4,5-dihydro-3-methyl-1,2,4-triazol-
5(lH)-one To a stirred mixture oE 12.0 g (0.047 mole) of l (3-methoxyphenyl) 4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(lH)-one (prepared from 3-methoxy-aniline using the method of Example 2, Steps B-~) in 75 mL of acetic acid was added 30.0 g (0.19 mole) of bromine. The mixture was heated at reflux for six hours, then cooled. The solvent was removed by dis-tillation, leaving a residue. This residue was dis-solved in diethyl ether, and the resultant solution was washed first with an aqueous 10% sodium thiosul-fate solution followed by water. The organic solution lS was dried over anhydrous magnesium sulfate and fil-tered. The filtrate was evaporated under reduced pressure, leaving a solid. This solid was triturated in petroleum ether and filtered to yield 17.4 g of 1-(2,4-dibromo-5-methoxyphenyl)-4-di~fluoromethyl-4,5-dihydro-~3-methyl-1,2,4-triazol-5(1H) one.
The nmr spectrum was consistent with the proposed structure.
~ s Step B 1-(2,4-Dibromo 5-hydroxyphenyl)-4-difluoro-methyl 4,5-dihydro-3-methy1-1,2,4-triazol-25~ 5(lH)-one ~ ;
A mixture of l7.2 g (0.042 mole)~of 1-(2,4-dibromo-5-methoxyphenyl)-4-difluoromethyl-~4,5-~dihydro-3-methyl- ~
1,2,4-triazol-5-(lH)-one; and 5~0.~6 g~(0.020 m~ole) of ~ -oro~ tr~ibromide in lOO mL of methylene chloride was 30~ stirred at room temperature for 18 hours.~ The mixture was washèd with 50 mL of water, a~nd the organic phase was dried~over anhydrous~Dagnesium sul~fate. This mix-i7 ture was filtered, and the filtrate was evaporated under reduced pressure to yield 16.1 g of 1-(2,4-di-bromo-5-hydroxyphenyl)-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-tria~ol-5-(lH)-one as a solid.
The nmr spectrum was consistent with the proposed structure.
Step C Ethyl 2-[2,4-dibromo-5-(4-difluoro~ethyl-4,5-dihydro-3-methyl-5-oxo-lH-1,2,4-triazol-l-yl)-phenoxy]propionate - 10 To a stirred solution of 1.25 g (0.0031 mole) of 1-(2,4-dibromo-5-hydroxyphenyl)-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one in 60 mL of N,N-dimethyl~ormamide was added 0.57 g (0.0033 mole) of ethyl 2-bromopropionate. The resultant mixture was heated at 130C for two hours, then was cooled. The solvent was evaporated from the mixture under reduced pressure, leaving a solid. This solid was dissolved in diethyl ether, and the solution was washed first with water, then with an aqueous 10% sodium hydroxide solution. The organic solution was dried over anhy-drous magnesium sulfate and filtered. The filtrate was evaporated under reduced pressure to yield 1.0 g of ethyl 2-[2,4-dibromo-~5-(4-difluoromethy}-4,5-di-hydro-3-methyl-5-oxo-lH-1,2,4-triazol-1-yl)phenoxy]
; ;25 ~ propio~nate as an oil, Compound 8.
The nmr spectrum was consistent with the proposed structure. ~ ~
Methylpropyl 2-[2,4-dlchloro-5-(4-difluoro-30 ~ methyl-4,5-dihydro-3-methyl-5-oxo-lH-1,2,4-triazol-l-yl)phenoxy]propionate~
: . . . .. . . , . ~ .. . . . .
~:~ - ~ , . - :.: ., . . :
~:6~ 7 To a stirred solution of 1.0 g (0.0025 mole) of 2-[2,4-dichloro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-S-oxo-lH-1,2,4-triazoll-yl)phenoxy]propionyl chloride (prepared in Example 6, Step A) in lS mL of sec-butanol was added 0.27 g (0.0027 mole) of tri-ethylamine. The reaction mixture was stirred at room temperature for 20 minutes, then heated at 70C for 1-1/2 hours. The mixture was allowed to cool and was stirred at ro~m temperature for approximately 18 hours. The solvent was removed by evaporation under reduced pressure, leaving a residue which was parti-tioned between deithyl ether and water. The organic phase was washed in succession with water, an aqueous 10~ sodium hydroxide solution, water, aqueous 10%
hydrochloric acid, a saturated aqueous sodium bicar-bonate solution, and water. The organic phase was dried over anhydrous magnesium sulfate, then fil-teréd. The filtrate was evaporated under reduced ~,~ pressure to yield 0.42 g of l-methylpropyl 2-[2,4-dichloro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-lH-1,2,4-triazol-1-yl)-phenoxy]propionate as an oil, Compound 12.
~ The nmr spectrum was consistent with the proposed P structure.
Compound B4 was;also prepared by the method of Example 8 from the acid chlorid~e of Compound A2 and 2-propyn-1-ol.
Example 9 Ethyl [2,4-dichloro-5-t4-difluoromethyl-4,5-30~ ~ dihydro-3-methyl-5-oxo-lH-1,2,4-triazol-1-yl)-phenoxy]EI~uoroace~ate ~ ~
To a stirred~mixture of 2.0 g~ (0.0065 mole) of 1-(2,4-~ ~ ,. .. . . .. .
:~Z~6~:i7 dichloro-5-hydroxyphenyl)-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one and 0.91 g (0.0065 mole) of ethyl chlorofluoroacetate in 50 mL of ethanol was added a solution of 0.15 g (0.0065 mole) of sodium in 5 mL of ethanol. The reaction mixture was heated at reflux for 34 hours. The mixture was cooled, and the sol~ent was removed by evaporation under reduced pressure, leaving a residue. This residue was dis-` solved in diethyl ether, and the solution was washed first with water, followed by an aqueous 10% sodium hydroxide solution. The organic phase was dried over anhydrous magnesium sulate, then filtered. The fil-trate was evaporated under reduced pressure to yield 0.95 g of ethyl [2,4-dichloro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-lH-1,2,4-triazol-1-yl)phenoxy]-fluroacetate as an oil, Compound 51.
- The nmr spectrum was consistent with~the proposed structure.
Example 10 Ethyl 2-[2,4-dichloro-5-(4-fluoromethyl-4,5-dihydro-3-methyl-5-oxo-lH-1,2,4-triazol-1-yl)-~; phenoxy]propionate Step A 1-[2j4-Dichloro-5~ methylethoxy)phenyl]-4-fluoromethyl-4,5-dihydro-3-methyl-1,2,4-25 ~ triazol-5(1H)-one A solution of 6.0 g (0.020;mole) of 1-[2,4-dichloro-5-(1 methylethoxy)phenyl]-4,5~-dihydro-3-methyl-1,2,4-tri~azol-5(1H)-one in~45 mL of N,N-dimethylformamide was added to 0.55 g (0.022 mo~le) of sodium hydride in ; 30~ 30~mL of N,~N-dimethylformamide. The reaction mixture was slirred~at~room temperature for 15~minutes.
The nmr spectrum was consistent with the proposed structure.
~ s Step B 1-(2,4-Dibromo 5-hydroxyphenyl)-4-difluoro-methyl 4,5-dihydro-3-methy1-1,2,4-triazol-25~ 5(lH)-one ~ ;
A mixture of l7.2 g (0.042 mole)~of 1-(2,4-dibromo-5-methoxyphenyl)-4-difluoromethyl-~4,5-~dihydro-3-methyl- ~
1,2,4-triazol-5-(lH)-one; and 5~0.~6 g~(0.020 m~ole) of ~ -oro~ tr~ibromide in lOO mL of methylene chloride was 30~ stirred at room temperature for 18 hours.~ The mixture was washèd with 50 mL of water, a~nd the organic phase was dried~over anhydrous~Dagnesium sul~fate. This mix-i7 ture was filtered, and the filtrate was evaporated under reduced pressure to yield 16.1 g of 1-(2,4-di-bromo-5-hydroxyphenyl)-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-tria~ol-5-(lH)-one as a solid.
The nmr spectrum was consistent with the proposed structure.
Step C Ethyl 2-[2,4-dibromo-5-(4-difluoro~ethyl-4,5-dihydro-3-methyl-5-oxo-lH-1,2,4-triazol-l-yl)-phenoxy]propionate - 10 To a stirred solution of 1.25 g (0.0031 mole) of 1-(2,4-dibromo-5-hydroxyphenyl)-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one in 60 mL of N,N-dimethyl~ormamide was added 0.57 g (0.0033 mole) of ethyl 2-bromopropionate. The resultant mixture was heated at 130C for two hours, then was cooled. The solvent was evaporated from the mixture under reduced pressure, leaving a solid. This solid was dissolved in diethyl ether, and the solution was washed first with water, then with an aqueous 10% sodium hydroxide solution. The organic solution was dried over anhy-drous magnesium sulfate and filtered. The filtrate was evaporated under reduced pressure to yield 1.0 g of ethyl 2-[2,4-dibromo-~5-(4-difluoromethy}-4,5-di-hydro-3-methyl-5-oxo-lH-1,2,4-triazol-1-yl)phenoxy]
; ;25 ~ propio~nate as an oil, Compound 8.
The nmr spectrum was consistent with the proposed structure. ~ ~
Methylpropyl 2-[2,4-dlchloro-5-(4-difluoro-30 ~ methyl-4,5-dihydro-3-methyl-5-oxo-lH-1,2,4-triazol-l-yl)phenoxy]propionate~
: . . . .. . . , . ~ .. . . . .
~:~ - ~ , . - :.: ., . . :
~:6~ 7 To a stirred solution of 1.0 g (0.0025 mole) of 2-[2,4-dichloro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-S-oxo-lH-1,2,4-triazoll-yl)phenoxy]propionyl chloride (prepared in Example 6, Step A) in lS mL of sec-butanol was added 0.27 g (0.0027 mole) of tri-ethylamine. The reaction mixture was stirred at room temperature for 20 minutes, then heated at 70C for 1-1/2 hours. The mixture was allowed to cool and was stirred at ro~m temperature for approximately 18 hours. The solvent was removed by evaporation under reduced pressure, leaving a residue which was parti-tioned between deithyl ether and water. The organic phase was washed in succession with water, an aqueous 10~ sodium hydroxide solution, water, aqueous 10%
hydrochloric acid, a saturated aqueous sodium bicar-bonate solution, and water. The organic phase was dried over anhydrous magnesium sulfate, then fil-teréd. The filtrate was evaporated under reduced ~,~ pressure to yield 0.42 g of l-methylpropyl 2-[2,4-dichloro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-lH-1,2,4-triazol-1-yl)-phenoxy]propionate as an oil, Compound 12.
~ The nmr spectrum was consistent with the proposed P structure.
Compound B4 was;also prepared by the method of Example 8 from the acid chlorid~e of Compound A2 and 2-propyn-1-ol.
Example 9 Ethyl [2,4-dichloro-5-t4-difluoromethyl-4,5-30~ ~ dihydro-3-methyl-5-oxo-lH-1,2,4-triazol-1-yl)-phenoxy]EI~uoroace~ate ~ ~
To a stirred~mixture of 2.0 g~ (0.0065 mole) of 1-(2,4-~ ~ ,. .. . . .. .
:~Z~6~:i7 dichloro-5-hydroxyphenyl)-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one and 0.91 g (0.0065 mole) of ethyl chlorofluoroacetate in 50 mL of ethanol was added a solution of 0.15 g (0.0065 mole) of sodium in 5 mL of ethanol. The reaction mixture was heated at reflux for 34 hours. The mixture was cooled, and the sol~ent was removed by evaporation under reduced pressure, leaving a residue. This residue was dis-` solved in diethyl ether, and the solution was washed first with water, followed by an aqueous 10% sodium hydroxide solution. The organic phase was dried over anhydrous magnesium sulate, then filtered. The fil-trate was evaporated under reduced pressure to yield 0.95 g of ethyl [2,4-dichloro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-lH-1,2,4-triazol-1-yl)phenoxy]-fluroacetate as an oil, Compound 51.
- The nmr spectrum was consistent with~the proposed structure.
Example 10 Ethyl 2-[2,4-dichloro-5-(4-fluoromethyl-4,5-dihydro-3-methyl-5-oxo-lH-1,2,4-triazol-1-yl)-~; phenoxy]propionate Step A 1-[2j4-Dichloro-5~ methylethoxy)phenyl]-4-fluoromethyl-4,5-dihydro-3-methyl-1,2,4-25 ~ triazol-5(1H)-one A solution of 6.0 g (0.020;mole) of 1-[2,4-dichloro-5-(1 methylethoxy)phenyl]-4,5~-dihydro-3-methyl-1,2,4-tri~azol-5(1H)-one in~45 mL of N,N-dimethylformamide was added to 0.55 g (0.022 mo~le) of sodium hydride in ; 30~ 30~mL of N,~N-dimethylformamide. The reaction mixture was slirred~at~room temperature for 15~minutes.
6~7 Chlorofluoromethane was added dropwise to the stirred reaction mixture by condensing the gas on a dry ice condenser. During the addition the mixture was heated slowly to 60C at which point the mixture began to reflux. The addition of chlorofluromethane was dis-continued, and the reaction mixture was allowed to cool to room temperature and stand for approximately 18 hours. Heating at reflux was resumed, and an addi-tional amount of chlorofluoromethane was added during a ten minute period. After complete addition, the reaction mixture was heated at reflux for one hour, then allowed to cool. The solvent was removed by dis-- tillation under reduced pressure, leaving a residue.
This resldue was partitioned between diethyl ether and water. The organic phase was washed first with lN
sodium hydroxide, then water. The organic solution was dried over anhydrous magnesium sulfate and filtered. The filtrate was evaporated under reduced pressure to yield 3.8 g of 1-[2,4-dichloro-5-(1-methylethoxy)phenyl]-4-fluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5tlH)-one as an oil.
The nmr spectrum was consistent with the proposed structure.
Step B 1-(2,4-Dichloro-5-hydroxyphenyl)-4-fluoro-methyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one ~ :
To 5mL of stirring concentrated~sulfuric acid was added portionwise 0.53 g (0.0016 mole) of 1-[2,4-di-chloro-5 (~1-methylethoxy)phenyI]-4-fluoromethyl-4,5-dihydro-3-methylrl,2,4-triazol-5tlH)-one. After complete addition, the mlxture was stirred at room temperature for 2.5 hours. The mixture was poured into 100 mL of;ice water and stirred for 30 minutes.
~ ::
~., :. ,, : - .
~2~6~7 The aqueous mixture was extracted with diethyl ether, and the extract was washed with water. The organic phase was dried over anhydrous magnesium sulfate and filtered. The filtrate was evaporated under reduced pressure to yield 0.34 g of 1-(2,4-dichloro-5-hydroxy-phenyl)-4-fluoromethyl-4,5-dihydro-3-methyl-19 2,4-triazol-5(1H)-one as a solid.
The nmr spectrum was consistent with the proposed structure.
This reaction was repeated using 2.8 g of 1-[2,4-dichloro-5-(1-methylethoxy~-4-fluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one, producing an addi-; tional 1.9 g of product.
Step C Ethyl 2-[2,4-dichloro-5-(4-fluoromethyl-4,5-dihydro-3-methyl-5-oxo-lH-1,2,4-tria-zol-l-yl)-phenoxy]propionate ~ .
A mixture of 0.56 g (0.0019 mole) of 1-(2,4-dichloro-5-hydroxyphenyl)-4-fluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one and 1.1 g (0.0076 mole) of anhydrous potassium carbonate in 15 mL of acetone was `~ stirred for 15 minutes. Sodium iodide (approximately 0.01 g) and 0.37 g (0.002 mole) of ethyl 2-bromo-propionate were added, and the resultant mixture was heated at~ reflux for 1.5 hours. ~The mixture was cooled and filtered. The filtrate was evaporated under reducéd pressure, leaving~ a residue.~ This resi-due was partitioned between diethyl ether and water.
~ The organic phase was washed with water, dried over g~ anhydrous magnesium sulfate, and filtered. The fil-~ trate was evaporated under reduced pressure, leaving ; ; an oil. This~oil was stirred in~ n-pentane, and the supernant was decanted, leaving an oily residue. The oil was dried at 70C under a stream of nitrogen to . :. :
~6~1~7 yield 0.70 g of ethyl 2-[2,4-dichloro-5-(4-fluoro-methyl-4,5-dihydro-3-methyl-5-oxo-lH-1,2,4-triazol-1-yl~phenoxy]propionate, Compound 13.
The nmr spectrum was consistent with the proposed structure.
Example 11 N-(4-Methylphenylsulfonyl)-2-[2-chloro-4-fluoro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-lH-l, 2,4-triazol-1-yl)phenoxy]propionamide A stirred mixture o~ 0.78 g (0.0021 mole) of 2-[2-chloro-4-~Iuoro-5-(4-difluoromethyl-4,5-dihydro-3 ~ methyl-5-oxo-lH-1, 2,4-triazol-1-yl)phenoxy]propionic - acid, 0.42 g (0.0021 mole) of p-toluenesulfonyl iso-; cyanate and 0.05 g (0.0004 mole) of 4-dimethylamino-- 15 pyridine in 50 mL of toluene was heated at re~lux for -approximately 18 hours. The mixture was allowed to cool to room temperature and was stirred for 24 hours. The solvent was removed by evaporation at reduced pressure to leave a residue. This residue was purified by column chromatography on silica gel, elut-ing with toluene:ethyl acetate (1:1). The appropriate fractions were combined and evaporated under reduced pressure to yield 0.7 g of N~4-methylphenylsulfonyl)-2-[2-chloro-4~:fluoro-5-t4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-lH-1~2~4-triazol-1-yl)phenoxy]propionamide as a solid, Compound C10.
The nmr spectrum was consistent with the proposed structure.
Compound C25 was prep;ared by the method of ; 30 Example ll using 2-chlorobenzenesulfonyl ~isocyanate.
.... . .. . .
~: :
~6~i7 Example 12 '~
2-[2-Chloro-4-fluoro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-lH-1,2,4-triazol-1-yl) ; phenoxy]propionic acid, sodium salt.
A mixture of 1.0 g (0.0027 mole) of 2-[2-chloro-4-fluoro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-lH-1,2,4-triazol-1-yl)phenoxy]propionic acid and 0.07 g (0.0027 molb) of sodium hydride in 30 mL of tetrahydrofuran was stirred at room temperature for lG approximately 18 hours. The solvent was removed by evaporation to yield 0.9 g o~ 2-[2-chloro-4-fluoro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-lH-1,2,4-~` triazol-l-yl) phenoxy]propionic acid, sodium salt as a solid, Compound A4.
Compounds C19 and C20 were prepared by the method of Example 12 ~rom compounds C18 and C10 respective-ly. Compound A6 was prepared by a method analogous to ; that of Example 12 from Compound A2, substituting iso-propylamine for sodium hydride.
~ ~Examele 13 2,4-Dl~chloro-5-(3-dlfluoromethyl-4,5-dihydro-4~-me~thyl-5-oxo-lH-1:,2,4-triazol-1~-yl)phenoxy]-acetami~de S~ep;A~ Ethyl difluoroacetylcarbamate ; -~
2~5~ ;During~a~30 minu~e~period~6~.4~g ~0.~55 mol;e) of thionyl~chloride was added;~to 5~0.0 g;(0.52 mole) of~
di1uoroacetic ac~id while~stirring.~ Gas evolved~dur-ng~the~ad~di~tlon was re~turned to t~he react~on mi~x~ure~
by~co~ndensatlon on~a~dry~ice c~ondenser.- AEter com-,.. . ~ . ., , , ., ... ~ ,. .. :. - .. . .
plete addition, the mixture was stirred at room tem-perature for approximately two hours. Urethane, 46.4 g (0~52 ~ole), was added and, after complete addition, the reaction mixture was heated at 60-70C for three hours. The mixture was cooled to room temperature and stirred for approximately 18 hours. The mixture was again heated at about 75C for two hours, then cooled. The mixture was evaporated under reduced pressure to leave an oily residue. This residue crystallized upon standing. The crystallized residue was washed with petroleum ether and filtered to yield 68.4 g of ethyl difluoroacetylcarbamate (mp 55-57C).
Step B 1-[2,4-Dichloro-5-(1-methylethoxy)phenyl]-3-difluoromethyl-4,5-dihydro-1,2,4-triazol-~ 15 5(1H)-one .- :' '. . ' , . .
To a stirred solution of 11.8 g (0.05 mole) of 2,4-di-chloro-5-(1-methylethoxy)phenylhydrazine and 10.0 g (0.06 mole) of ethyl difluoroacetylcarbamate in 130 mL
of xylene was added 2.5 g (0.02 mole) of phosphorus pentoxide. After complete addition the mixture was , heated at reflux for 1.5 hours then allowed to cool to room temperature for approximately 18 hours. The ~; reaction mixture was decanted from a dark residue in the reaction flask and washed with watèr. The washed mixture was~ extracted with a 10% aqueous sodium hydroxide solution. The basic extract was made acidic with concentrated hydroch~loric acid to form~an oily precipitate. This aqueous phase was decanted from the oily~residue and fresh water added to wash the resi-due. This residue was dissolved in l60 mL of methyl-ene~chloride and Eiltered through a celite pad. The filtrate was dried over anhydrous magnesium sulfate and Eiltered. The filtrate was evaporated under . . . . . ... . .. .. .. ..
~, :- . ,, .................. , . , ~ .
~ , : , , :
6~i7 reduced pressure to leave a semi-solid residue. The residue was triturated with approximately 125 ~L of petroleum ether to provide 8.2 g of 1-[2,4-dichloro-S-(l-methylethoxy)phenyl]-3-difluoromethyl-4,5-dihydro-1,2,4-triazol-S(lH)-one.
Step C 1-[2,4-Dichloro-5-(1-methylethoxy)phenyl]-3-difluoromethyl-4,5-dihydro-4-methyl-1,2,4-triazol-5(1H)-one.
A stirred mixture of 4.0 g (0.012 mole) of 1-[2,4-di-chloro-S-(l-methylethoxy)phenyl]-3-difluoromethyl-4,5-dihydro-1,2,4-triazol-S(lH) one and 4.1 g (0.03 mole) of potassium carbonate in 160 mL of acetone was heated at reflux for O.S hours then cooled to about 50C.
. Methyl iodidej 8.4 g (0;06 mole), wa.s added and the mixture stirred at 45 for one hour then at reflux for one hour. The mixture was cooled to room temperature and evapcrated under reduced pressure to leave an - oil. This oil was partitloned between methylene chloride and water. The organic phase was washed with a 10% aqueous sodium hydroxide solution and then dried - over anhydrous magnesium sulfate. The mixture was filtered and the filtrate evaporated under reduced pressure to leave an oil. This oil solidified when `
stirred with petroleum ether and upon filtration pro-Yided 2.6 g of 1-[2,4-dichloro-5-(1-methylethoxy)-; ~ phenyl]-3-difluoromethyl-4,5-dihydro-4-methyl 1,2,4-triazol-S-(lH)-one (mp 95-97C). ~ ~
Step D 1-(2,4-Dichloro-5-hydroxyphenyl)-3-difluoro-methyl-4,5-dihydro-4-methyl-l,Z,4-triazol-30~ S(lH)-one Hydrolysis of 2.2 g (0.0063 mole~ of l-t2,i-dichloro-., .. i . ~ . . , . . . .. .... .. , .,, . ,. , ... , ~ .. . .
~6~7 5-(1-methylethoxy)phenyl]-3-difluoromethyl-4,5-dihydro-4-methyl-1,2,4-triazol-5(1H)-one in 5 mL of concen-trated sulfuric acid produced 1.4 g of 1-(2,4-di-chloro-5-hydroxyphenyl)-3-difluoromethyl-4,5-dihydro-4-methyl-1,2,4-triazol-5(1H)-one (mp 176-179C).
Step E [2,4-Dichloro-5-(3-difluoromethyl-4,5-dihydro-4-methyl-5-oxo-lH-1,2,4-triazol-1-yl)phenoxy]acetamide In a manner similar to Example 1, the reaction of 0.72 g (0.00023 mole) of 1-(2,4-dichloro-5-hydroxyphenyl)-3-difluromethyl-4,5-dihydro-4-methyl-1,2,4-triazol-5(1H)-one, 0,32 g (0.00023 mole) of potassium carbon-ate, and 0.47 g (0.00025 mole) of iodoacetamide in 5 i mL of acetone produced 0.69 g of [2,4-dichlo~ro-5-(3-:~ 15 difluoromethyl-4,5-dihydro-4-methyl-5-oxo-lH-1,2,4-triazol-l-yl)phenoxy]acetamide (mp 190-193.50Cj.
The nmr spectrum was consistent with the proposed ~'~ structure.
~, The following compounds were prepared~by~the pro-cess of S. Chandrasekaran~et al., Synthetic Communica-tions, 12(9), 727-731 (1982) from Compound A2 and the following reagents.
Compound~ Reagent~
~- B8 ~ tetrahydrofurfuryl alcohol B9 methyl hydroxyacetate B10 ~ 2-methyl-3,3,4,4-tetrafl;uoro-2-butanol Bl2 furfuryl alcohol B13 ~ N,N-dimethylethanolamine B14 ~ 3-hydroxytetrahydrofuran 0 Bl5~ ~ phenol B17 ~ ethanethiol Bl8~ ~ ethyl 2-mercap`toacetate B30 ~trifluoroethanol B31 ~ acetone cya~nohydrin ~ B32 ~benzyl alcohol B33 ~ Z-propanethiol Cll ~ ; O,N-~dimethylhydroxylamine hydrochloride ;~6~ i7 Compound Reagent C12 (2-propynyl)amine C13 aniline C14 dimethylamine Cl5 diethylamine C16 ethylamine hydrochloride C17 glycine methyl ester hydrochloride C22 2-amino-2-methylpropionitrile C23 N-methylaniline Compound B25 was prepared by the method of Lonord et al., J. Or~.. Chem. 27,282-284 (1962) from Compound B23.
Compound A5 was prepared by the hydrolysis of Compound 22 using the procedure described by Kurtev et al., Synthesis tl975), 106-108.
Characterizing properties of some of the com-pounds oE the invention are given in Table 6 below.
~xample 14 N-(2,5-dimethoxyphenylsulfonyl)-2-[2-chloro-4-fluoro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-lH-1,2,4-triazol-1-yl)phenoxy]propionamide Step A~ 2,5-Dimethoxyphenylsulfonamide To a stlrred solution of~ 5~.0 g (0.063 mole) of ;~
2,~5-dimethoxybenzenesulfonyl chloride in 150 mL ~of 25~ ~ tet~rahyd~rofuran was added~dropwlse~80 mL of~ammonia (28% aqueous solution).~ ~Afte~r~complete addition the~
mixture was allowed to stir ~or 1.75 hours at room tempe`rature~ Upon~standing the mi~xture separated into two phases. The~organi~c phase was removed from the 30~ aqueous~phase~and~was~evaporated~under reduced pres-s~ure to~leave~a ~so~lid~ residue. This residue~was~
~ rec~rystalli~zed ~rom hot water~(125 mL) and ethanol s~ (40~mL)~t~o~yield 13.1 g o{ 2,~5-dlmethoxyphenylsulfon-~ ami~de~(mp~ i~46.5-148.5). ~
The nmr spectrum was consistent with the proposed structure.
Step B N-(2,5-Dimethoxyphenylsulfonyl)-2-bromo-propionamide A stirred mixture of 7.0 g tO.032 mole) of 2,5-dime~h-oxyphenylsulfonamide in 10 mL of 2-bromopropionyl chloride was heated at reflux for 40 minutes then allowed to cool to room temperature. The resultant solution was poured into petroleum ether. Crystals formed a~ter scratching the sides of the flask and - we~re collected by filtration. The filter cake was `~ washed four times with fresh petroleum ether to yield 10.3 g of N-(2,5-dimethoxyphenylsulfonyl)-2-bromo-propionamide (mp 116-118C).
The nmr spectrum was consistent with the proposed - ~ structure. ~
Step C N-(2.5-Dimethoxyphenylsulfonyl)-2-[2-chloro-4-fluoro-5-;(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-lH-1,2,4-triazol-l-yl)phenoxy]propionamide To~ a stirred solution of 0.~75 g (0.0026 mole3 of 1-(4-chloro-2-fluoro-5-hydroxyphenyl)-4-difluoro-methyl-4,5-dihyd~o-3-methyl-1,2,4-triazol-5(1H)-one and 0.89 g~(0.0026 mole) of~N-(2~,5-dlmethoxyphenyl-~; su~lfony1)-~2-bro~mop`ropionamide~ in 50 mL~of~ acetone was added~1.04 g (0.0026 mo1e) of potassium carbonate.
After complete addition the mixture was heated~at 45C
for ~two~da~y 5. The~resultant~mixture was cooled and the;solvent was removed by ;evaporation under reduced 3~0~ pressure~to leave a residue~ This ~residue was~dis-solved ln l00 mL~o wate~r~ The aqueous solution was`~
126 ~ 667 acidified by the dropwise addition of concentrated hydrochloric acid producing a precipitate. The preci-pitate was collected by filtration. The filter cake was washed with water and then dried under reduced pressure to leave 1.23 g of N-(2,5-dimethoxyphenylsul-fonyl)-2-[2-chloro-4-fluoro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-lH-1,2,4-triazol-1-yl)phenoxy]-propionamide tmp 168-172C) Compound C90.
The nmr spectrum was consistent with the proposed structure.
Example 15 ~ 1-(4-Chloro-2-fluoro-5-methoxyphenyl)-4,5--~ dihydro-3-methyl-1,2,4-triazol-5(1H)-one as an intermediate ~. . . .
Step A N'-(4-Chloro-2-fluoro-5-methoxyphenyl)-~ acetamidrazone "~ A stirred mixture of 1.91 g (0.01 mole) of 4-chloro-2-fluoro-5-methoxyphenylhydrazine and 1.97 g (0.01 mole) of 3-(1-iminoethylmercapto)-1-propanesulfonic acid, inner salt, (prepared by the method of Reid et al, Ann. Chem. 676, 114 (1964)) in 5~0 mL of anhydrous ~f ethanol was heated at reflux for 1.25 hours. The mix-ture was cooled and evaporated under reduced pressure to leave 3.96 g of a residue. A portion~ of th~is resi-25 ~ due, 3.33~g,~was dissolved in ~50 mL of water. The resultant cloudy solution was~filtered through a pad of celite and the filtrate was~extracted with meth-ylene chloride. The clarlfied~aqueous solution was basified with approximately 8~mL of an aqueous 10%
30~ ~ ~sodium hydroxide solution. An oiI precipitated from he~basic mixture and slowly solidified. This solid :- , ~6~7 was collected by filtration. The filter cake was washed with water to yield 1.31 g of N'-(4-chloro-2-fluoro-5-methoxyphenyl)acetamidrazone (mp 106-107C).
- The nmr analysis was consistent with the proposed structure.
Analysis calc'd -for CgHllClFN30: C 46.66, H 4.79, N 18.14 Found: C 46.10, H 4.81, N 17.70 ,.
Step B 1-(4 Chloro-2-fluoro-S-methoxyphenyl)-4,5-dihydro-3-methyl-1,2,4-triazol-5(lH)-one A solution of 1.71 g (0.0086 mole) of trichloromethyl chloroformate in 5 mL of toluene was added dropwise to a stirred solution of 1.0 g (0.0043 mole) of N'-(4-chloro-2-fluoro-5-methoxyphenyl)acetamidrazone in 50 mL of toluene. After complete addition the mixture was stirred at room temperature for ~ive minutes then was heated slowly until a slow reflux was obtained.
. , Reflux was maintained for approximately 15 minutes.
~ The mixture was cooled and evaporated under reduced pressure to leave 1.22 g of a~ solid. Approximately 1.0 g of this solid was dissolved in 100 mL of methylene chloride. The resultant solution was fil-tered and the filtrate was extracted with three 25 mL
portions of an aqueous 10% sodium~ hydroxide solution followed by three 25 mL portions of lN sodium hydroxide. Each set of three similar extracts were combined and washed with methylene chloride. Both of the washed extracts were acidified with concentrated hydrochloric acid producing a precipitate from each.
The~solids~were collected by fi~ltrat~on to~provide 0.3 g and 0.12 g, from the 10% and lN base solutions respectlvely, of 1-(4-chloro-2-fluoro~-S-methoxy-:
"~ ~ ,, :,, :
.
i7 phenyl)-4,5-dihydro-3-methyl-1,2,4-triazol-5tlH)-one (mp 209-211C).
The nmr spectrum was consistent with the proposed structure.
Example 16 1-(2,4-Dichloro-5-hydroxyphenyl)-3-chloro-di~luoromethyl-4,5-dihydro-4-methyl-1,2,4-triazol-5(1H)-one as an intermediate ~Step A N'-[2,4-Dichloro-5-(1-methylethoxy)phenyl]-;~ lO chlorodi~luoroacetamidrazone :
~ A stirred solution o~ 9.4 g (0.04 mole) of 2,4-di-- ~ chloro-5-(1-methylethoxy)phenylhydrazine in 3S0 mL of absolute methanol was cooled to 0. Gaseous chlorodi-luoroacetonitrile (8.0 g, 0.07;mole) was addéd to the mixture. After complete addition the mixture was ~ allowed to warm to room temperature and stir ~or 3.5 ; ~ hours. The stirring was stopped and the mixture stood at room temperature for two days. The solvent was ~ evaporated from the mixtur~e~under reduced pressure to ;~ 20 leave~13.86 g of N'-~2,4-dichloro-5-(1-methyleth-oxy)phenyl]chlorodifluoroacetamidrazone as an oily residue.
Step B ~ 1-[~2,4-Dichloro-~5-(1-methylethoxy?phenyl]-3-chlorodifluo~romethyl-4,~5-dihydro-i,2,4-25~ triazol-5~1H~-one ~ ;
ln~a manner slmllar to Example I5, Step~B,~the reac-tion~of 13.86~g of``the~oily residue~Erom Step A plus 2.7~g~of~s`i~milar material`prepared in a separate experiment and l9.87 g~(0.1 mo~1e) of trichloromethyl ~6~
chloroEormate in 600 mL of toluene produced 5.4 g of 1-[2,4-dichloro-5-(1-methylethoxy)phenyl]-3-chlorodi-fluoromethyl-4,5-dihydro-1,2,4-triazol-5(1H)-one (mp 115-119C).
The nmr spectrum was consistent with the proposed structure.
Step C 1-[2,4-Dichloro-5-(1 methylethoxy)phenyl]-3-chlorodifluoromethyl-4,5-dihydro-4-methyl-1,2,4-triazol-5(1H)-one In a manner similar to Example 13, Step C, the reaction o~ 4.0 g (0.011 mole) of 1-~2,4-dichloro-5-;~ (l-methylethoxy)phenyl]-3-chlorodifluoromethyl-4,5-di-~; hydro-1,2,4-triazol-5(1H)-one, 4.26 g (0.03 mole) of ;~ methyl iodide, and 2.07 g ~(0.015 mole) of potassium carbonate in 40 mL of aceto~e provided 3.74 g of 1-[2,4-dichloro-5-(1-methylethoxy)phenyl]-3-chlorodi-~luoromethyl-4,5-dihydro-4-methyl-1,2,4-triazol-S(lH)-one as a solid. Recrystallization of a small portion of this solid from ethanol and water provided a pale yellow solid, mp 69-72C.
The nmr spectrum was consistent with the proposed ~; structure.
; Analysis calc'd for O2: C 40-39, H 3.13, N 10.87 Found: C 40.92, H 3.28, N 10.96.
Step~D ~ 1-(2,4-Dichloro-5-hydroxyphenyl)-3-; chlorodifluoromethyl-4,5-dihydro~4-nethyl-1,2,4-~triazol-5(1H)-one ~
I-Iydrolysls oE 2.6 g (0.0067 mole) of 1-[2,4-dlchloro-30 ~ ;5-(1-methylethoxy)phenyl]-3-chlorodifluoromethyl-4,5-i6~6~7 dihydro-4-methyl-1,2,4-triazol-5(1H)-one in 10 mL o~
concentrated sulfuric acid produced 2.17 g of 1-(2,4-dichloro-5-hydroxyphenyl)-3-chlorodifluoromethyl-4,5-dihydro-4-methyl-1,2,4-triazol-5(lH)-one as a solid (mp 146-148C).
The nmr spectrum was consistent with the proposed structure.
Analysis calc'd for CloH6C13F2N3O2: C 3~.86, H 1.76, N 12.20 Found: C 35.30, H 1.59, N lZ.25 HERBICIDAL ACTIVITY
The plant test species used in demonstrating the herbicidal activity of compounds of this invention include cotton (Gossypium hirsutum var. Stoneville), soybean (Glycine max var. Williams), field corn (Zea mays var. Agway 595S), wheat (Triticum aestivium var.
Prodax), rice (Oryza sativa), field bindweed (Convol-vulus arvensis), morningglory (Ipomea lacunosa or Ipomea hederacea, velvetleaf (Abutilon theophrasti), barnyardgrass (Echinochloa crus g~li), green foxtail ~, (Setaria viridis), and johnsongrass (Sorghum hale-~), yellow nutsedge (Cyperus esculentus).
Seeds or tubers of the plant test species were plant~ed in ~urrows in steam sterilized sandy loam soil ~ contained in disposable fiber flats. A topping soil o~ equal porti~ons of sand and sandy loam soil was placed un~iformly on top of each flat to a depth of approximately 0.5 cm.
The flats for the preemergence test were watered, then drenched with the appropriate~amount of a solu-tion of the test compound in a mixture of acetone and .~, :
water containing a small ~amount (up to 0.5% v/v) of sorbitan monolaurate emulsifier/solubilizer. The , :., :
concentration of the test compound in solution was varied to give a range of application rates, generally : ~
,.,,~ ~, ~6~66~
8.0 kg/ha and submultiples thereof. The flats were placed in a greenhouse and watered regularly at the soil surface for 21 days at which time phytotoxicity data were recorded.
The flats for the postemergence test 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 con-taining up to 0.5% sorbitan monolaurate. After spray-ing, the foilage was kept dry for 24 hours, then watered regularly for 21 days, and phytotoxicity data recorded.
Phy~oto~icity data were taken either as percent kill or percent control. Percent control was deter-mined by a method similar to the O 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:
: -, ~
~ :
; ~ ~ ~ .. .. ... .. . .. ... ...
Herbicide Rating System Rating Description Percent of Main Crop Weed Control ~ Description Description.
0 No effect No crop No weed reduction control _ or iniury _ _ __ _ _ - 10 Slight dis- Very poor weed coloration control or stunting Slight Some dis- Poor weed : effect coloration, control stunting or stand loss Crop injury Poor to defi-more pronounced cient weed ~.
but not lasting control _ _ . _ _ _ _ _ .. . ... .... ..
::. 40 Moderate injury, Deficient weed ~: . - crop usually control recovers : 50 ~oderate Crop injury Deficient to effect more lasting, moderate weed recovery control ~.
: : 60 Lasting crop Moderate weed : injury no con~rol recovery _ _ _ : 70 Heavy injury and Control some-~ : stand:loss: : what l:e~ss than :~ : satisfactory : 80 : :Severe Crop nearly des- Satisfactory : troyed:a few to good weed : survivors control 90 ; ~ ~ Only occasional Very good:to live~plants left excetlIlnt 100 Complete Complete crop~ Complete weed effect ~destruction destruction :~;6~ 7 Herbicidal data at selected application rates are given for various compounds of the invention in the tables below. The test compounds are identified in the tables of herbicidal data below by n~mbers which correspond to those used above.
In the Tables of herbicidal data below:
"kg/ha" is kilograms per hectare, "% K" is percent kill, and "~ C" is percent control.
For herbicidal application, the active co~pounds as above defined are formulated into herbicidal com-positions 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, recog-nizing the fact that the formulation and mode of application of a toxicant may a~fect the activity of the material in a given application. Thus, for agricultural use the present herbicidal compounds may be formulated as granules of relatively large particle size, water-soluble or water-dispersible granules, as ' powdery dusts, as wettable powders, as emulsifiable concentrates, as solutions or as any of several other known types of formulations, depending on the desired 25~ mode of application.
For preemergence application these herbicidal composltions are usually applied either as sprays, dusts1 or granuies to the~areas in which suppression of vegetation is desired. For postemergence control of established plant growth, sprays or dusts are most commonly~us;ed. These formulations may contain as lit~tle as 0.5% to as much as 95% or more by weight of active ingredient.
Dusts re free flowing admixture~s of~the active `` 35 ~ ingredient with finely divided solids such as talc, '7 - so -natural clays, kieselguhr, f~ours such as walnut shell and cottonseed flours, and other organic and inorganic solids which act as dispersants and carriers for the toxicant; these finely divided solids have an average particle size of less than about 50 microns. A typi-cal dust formulation useful 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 dispersant. 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 absor-bent, ~readily wet inorganic diluents. Wettable pow-ders 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 ~; wetting, dispersing or emulsifying agent to facilitate dispersion. For example, a useful wettable powder - ~ ~ormulation contains 80.8 parts of the herbicidal -~ compound, 17.9 parts of Palmetto clay, and 1.0 part of sodium lignosulfonate and O.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 facili-tate dispersion on the foliage and absorption by the plant.
~ Other~ useful formulations for herbicidal applica--~ tions are emulsifiable concentrates. Emulsifiable concentrates~are homogeneous liquid or paste composi-tions dispersible in water or other dispersant, and may consist entirely of the herbicidal compound and a : ~ : : :
~.: , : . :. . . ~ : ..
.: ... . .~ ~,. .. : ; --~
i6~'7 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 concen- ~
trates are dispersed in water or other liquid carrier, and normally applied as a spray to the area to be treated. The percentage by weight of the essential - active ingredient may vary according to the manner in which the composition is to be applied, but in general comprises 0.5 to 95% of active ingredient by weight of the herbicidal composition.
Typical wetting, dispersing or emulsifying agents used in agricultural formulations include, for exam-ple, the alkyl and alkylaryl sulfonates and s~lfates and their sodium salts; polyhydric alcohols; and other ~; types of surface active agents, many of which are ; available in commerce. The surface active agent, when used, normally comprises 1% to 15% by weight of the herbicidal composition.
~ Other useful formulations for herbicidal applica-tions include simple solutions of the active ingre-dient in a dispersant in which it is completely solu-ble at the desired concentration, such as acetone, aIkylated naphthalenes, xylene or other organic sol-25~ vents. Granular formulations, wherein the toxicant is carried on~irelatively coarse particles,~are of parti- ;
cular utility for aerial;distribution 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 vapor-i2ation of;a low boiling di~spers;ant solvent carrier,~
such~as~the~Freons, may also be~used. Water-soluble or~water-~di~spersible granules are a3so useful `formula-tions~for herbicidal application of the present com-p-un1s. Su=h granulA- formul~tlons ~r~ tr-e-'l-win~:
~26~6~7 non-dusty, and readily water-soluble or water-misci-ble. The soluble or dispersible granular formulations described in U.S. patent No. 3,920,442, ~ e~
~ ~e~ F~ e~ are useful herein with the pre-sent herbicidal compounds.
The active herbicidal compounds o~ this invention may be formulated and/or applied ~ith insecticides, fungicides, nematicides, plant growth regulators, fertilizers, or other agricultural chemicals and may be used as effective soil sterilants as well as selec-tive herbicides in agriculture. In applying an active ; compound o~ this invention, whether formulated alone or with other agricultural chemicals, an effective amount and concentration of the active compound is of course employed; the amount may be as low as, for example, 7 g/ha or lower.
The active herbicidal compounds of this invention may be used in combination with other herbicides, e.g.
they may be mixed with, say, an equal or lar~er amount o~ a known herbicide such as chloroacetanilide -;~ herbicides such as 2-chloro-N-t2,6-diethylphenyl)-N-(methoxy~ethyl)acetamide (alachlor),;2-chloro-N-(2--` ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl)-acetamide (metolachlor), and N-chloroacetyl-N-(2,6-diethylphenyl)gIycine (diethatyl-ethyl); benzothia-diazinone herbicides such as 3-(1-methylethyl)-(lH) 2,1,3-benzothiadiazin-4-(3H)-one-2,2-dioxide (benta zon); ~triazlne herbicides such as 6-chloro-N-ethyl-N-(l-methylethyl)-1,3,5-triazine-2,4-diamine (atra-;30 zine),; and 2- [4-chloro-6-(ethylamino)-1,3,5-triazin-2-yl]-amino -2-methylpropanenitrile ~cyanazine);
dinitrolaniline herbicid~es such as 2,6-dinitro-N,N-dipropyl-4-(trifluoromethyl)benzeneamine (triflura-lin); and aryl urea herbicides such as N'-(3,4-di-~ : :
:~2~6~7 - ~3 -chlorophenyl)-N,N-dimethylurea (diuron) and N,N-dimethyl-N'-[3-(trifluoromethyl)phenyl]urea (fluo-meturon).
It is apparent that various modifications may be made in the formulation and application of the com-: pounds of this invention, without departing from the inventive concepts herein, as defined in the following claims.
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i6ç~7 TABLE_l Percent Control Pre-Emergent Post-Emer~ent PLANT A B A B
Cotton 50 0 90 40 Soybean 10 0 0 10 Corn 0 Rice 50 20 40 0 Wheat 30 0 40 20 Field Bindweed 60 0 40: 0 Morningglory 20 0 60 10 Velvetlea~ 100 0 100 0 Barnyardgrass 70 0 90 . 0 Green foxtail 100 70 90 ~ ~ 0 Johnsongrass 40 0 10 : 0 Yellow nutsedge 30 0 10 0 3 o o 8 owmd ~
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This resldue was partitioned between diethyl ether and water. The organic phase was washed first with lN
sodium hydroxide, then water. The organic solution was dried over anhydrous magnesium sulfate and filtered. The filtrate was evaporated under reduced pressure to yield 3.8 g of 1-[2,4-dichloro-5-(1-methylethoxy)phenyl]-4-fluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5tlH)-one as an oil.
The nmr spectrum was consistent with the proposed structure.
Step B 1-(2,4-Dichloro-5-hydroxyphenyl)-4-fluoro-methyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one ~ :
To 5mL of stirring concentrated~sulfuric acid was added portionwise 0.53 g (0.0016 mole) of 1-[2,4-di-chloro-5 (~1-methylethoxy)phenyI]-4-fluoromethyl-4,5-dihydro-3-methylrl,2,4-triazol-5tlH)-one. After complete addition, the mlxture was stirred at room temperature for 2.5 hours. The mixture was poured into 100 mL of;ice water and stirred for 30 minutes.
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~., :. ,, : - .
~2~6~7 The aqueous mixture was extracted with diethyl ether, and the extract was washed with water. The organic phase was dried over anhydrous magnesium sulfate and filtered. The filtrate was evaporated under reduced pressure to yield 0.34 g of 1-(2,4-dichloro-5-hydroxy-phenyl)-4-fluoromethyl-4,5-dihydro-3-methyl-19 2,4-triazol-5(1H)-one as a solid.
The nmr spectrum was consistent with the proposed structure.
This reaction was repeated using 2.8 g of 1-[2,4-dichloro-5-(1-methylethoxy~-4-fluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one, producing an addi-; tional 1.9 g of product.
Step C Ethyl 2-[2,4-dichloro-5-(4-fluoromethyl-4,5-dihydro-3-methyl-5-oxo-lH-1,2,4-tria-zol-l-yl)-phenoxy]propionate ~ .
A mixture of 0.56 g (0.0019 mole) of 1-(2,4-dichloro-5-hydroxyphenyl)-4-fluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one and 1.1 g (0.0076 mole) of anhydrous potassium carbonate in 15 mL of acetone was `~ stirred for 15 minutes. Sodium iodide (approximately 0.01 g) and 0.37 g (0.002 mole) of ethyl 2-bromo-propionate were added, and the resultant mixture was heated at~ reflux for 1.5 hours. ~The mixture was cooled and filtered. The filtrate was evaporated under reducéd pressure, leaving~ a residue.~ This resi-due was partitioned between diethyl ether and water.
~ The organic phase was washed with water, dried over g~ anhydrous magnesium sulfate, and filtered. The fil-~ trate was evaporated under reduced pressure, leaving ; ; an oil. This~oil was stirred in~ n-pentane, and the supernant was decanted, leaving an oily residue. The oil was dried at 70C under a stream of nitrogen to . :. :
~6~1~7 yield 0.70 g of ethyl 2-[2,4-dichloro-5-(4-fluoro-methyl-4,5-dihydro-3-methyl-5-oxo-lH-1,2,4-triazol-1-yl~phenoxy]propionate, Compound 13.
The nmr spectrum was consistent with the proposed structure.
Example 11 N-(4-Methylphenylsulfonyl)-2-[2-chloro-4-fluoro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-lH-l, 2,4-triazol-1-yl)phenoxy]propionamide A stirred mixture o~ 0.78 g (0.0021 mole) of 2-[2-chloro-4-~Iuoro-5-(4-difluoromethyl-4,5-dihydro-3 ~ methyl-5-oxo-lH-1, 2,4-triazol-1-yl)phenoxy]propionic - acid, 0.42 g (0.0021 mole) of p-toluenesulfonyl iso-; cyanate and 0.05 g (0.0004 mole) of 4-dimethylamino-- 15 pyridine in 50 mL of toluene was heated at re~lux for -approximately 18 hours. The mixture was allowed to cool to room temperature and was stirred for 24 hours. The solvent was removed by evaporation at reduced pressure to leave a residue. This residue was purified by column chromatography on silica gel, elut-ing with toluene:ethyl acetate (1:1). The appropriate fractions were combined and evaporated under reduced pressure to yield 0.7 g of N~4-methylphenylsulfonyl)-2-[2-chloro-4~:fluoro-5-t4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-lH-1~2~4-triazol-1-yl)phenoxy]propionamide as a solid, Compound C10.
The nmr spectrum was consistent with the proposed structure.
Compound C25 was prep;ared by the method of ; 30 Example ll using 2-chlorobenzenesulfonyl ~isocyanate.
.... . .. . .
~: :
~6~i7 Example 12 '~
2-[2-Chloro-4-fluoro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-lH-1,2,4-triazol-1-yl) ; phenoxy]propionic acid, sodium salt.
A mixture of 1.0 g (0.0027 mole) of 2-[2-chloro-4-fluoro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-lH-1,2,4-triazol-1-yl)phenoxy]propionic acid and 0.07 g (0.0027 molb) of sodium hydride in 30 mL of tetrahydrofuran was stirred at room temperature for lG approximately 18 hours. The solvent was removed by evaporation to yield 0.9 g o~ 2-[2-chloro-4-fluoro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-lH-1,2,4-~` triazol-l-yl) phenoxy]propionic acid, sodium salt as a solid, Compound A4.
Compounds C19 and C20 were prepared by the method of Example 12 ~rom compounds C18 and C10 respective-ly. Compound A6 was prepared by a method analogous to ; that of Example 12 from Compound A2, substituting iso-propylamine for sodium hydride.
~ ~Examele 13 2,4-Dl~chloro-5-(3-dlfluoromethyl-4,5-dihydro-4~-me~thyl-5-oxo-lH-1:,2,4-triazol-1~-yl)phenoxy]-acetami~de S~ep;A~ Ethyl difluoroacetylcarbamate ; -~
2~5~ ;During~a~30 minu~e~period~6~.4~g ~0.~55 mol;e) of thionyl~chloride was added;~to 5~0.0 g;(0.52 mole) of~
di1uoroacetic ac~id while~stirring.~ Gas evolved~dur-ng~the~ad~di~tlon was re~turned to t~he react~on mi~x~ure~
by~co~ndensatlon on~a~dry~ice c~ondenser.- AEter com-,.. . ~ . ., , , ., ... ~ ,. .. :. - .. . .
plete addition, the mixture was stirred at room tem-perature for approximately two hours. Urethane, 46.4 g (0~52 ~ole), was added and, after complete addition, the reaction mixture was heated at 60-70C for three hours. The mixture was cooled to room temperature and stirred for approximately 18 hours. The mixture was again heated at about 75C for two hours, then cooled. The mixture was evaporated under reduced pressure to leave an oily residue. This residue crystallized upon standing. The crystallized residue was washed with petroleum ether and filtered to yield 68.4 g of ethyl difluoroacetylcarbamate (mp 55-57C).
Step B 1-[2,4-Dichloro-5-(1-methylethoxy)phenyl]-3-difluoromethyl-4,5-dihydro-1,2,4-triazol-~ 15 5(1H)-one .- :' '. . ' , . .
To a stirred solution of 11.8 g (0.05 mole) of 2,4-di-chloro-5-(1-methylethoxy)phenylhydrazine and 10.0 g (0.06 mole) of ethyl difluoroacetylcarbamate in 130 mL
of xylene was added 2.5 g (0.02 mole) of phosphorus pentoxide. After complete addition the mixture was , heated at reflux for 1.5 hours then allowed to cool to room temperature for approximately 18 hours. The ~; reaction mixture was decanted from a dark residue in the reaction flask and washed with watèr. The washed mixture was~ extracted with a 10% aqueous sodium hydroxide solution. The basic extract was made acidic with concentrated hydroch~loric acid to form~an oily precipitate. This aqueous phase was decanted from the oily~residue and fresh water added to wash the resi-due. This residue was dissolved in l60 mL of methyl-ene~chloride and Eiltered through a celite pad. The filtrate was dried over anhydrous magnesium sulfate and Eiltered. The filtrate was evaporated under . . . . . ... . .. .. .. ..
~, :- . ,, .................. , . , ~ .
~ , : , , :
6~i7 reduced pressure to leave a semi-solid residue. The residue was triturated with approximately 125 ~L of petroleum ether to provide 8.2 g of 1-[2,4-dichloro-S-(l-methylethoxy)phenyl]-3-difluoromethyl-4,5-dihydro-1,2,4-triazol-S(lH)-one.
Step C 1-[2,4-Dichloro-5-(1-methylethoxy)phenyl]-3-difluoromethyl-4,5-dihydro-4-methyl-1,2,4-triazol-5(1H)-one.
A stirred mixture of 4.0 g (0.012 mole) of 1-[2,4-di-chloro-S-(l-methylethoxy)phenyl]-3-difluoromethyl-4,5-dihydro-1,2,4-triazol-S(lH) one and 4.1 g (0.03 mole) of potassium carbonate in 160 mL of acetone was heated at reflux for O.S hours then cooled to about 50C.
. Methyl iodidej 8.4 g (0;06 mole), wa.s added and the mixture stirred at 45 for one hour then at reflux for one hour. The mixture was cooled to room temperature and evapcrated under reduced pressure to leave an - oil. This oil was partitloned between methylene chloride and water. The organic phase was washed with a 10% aqueous sodium hydroxide solution and then dried - over anhydrous magnesium sulfate. The mixture was filtered and the filtrate evaporated under reduced pressure to leave an oil. This oil solidified when `
stirred with petroleum ether and upon filtration pro-Yided 2.6 g of 1-[2,4-dichloro-5-(1-methylethoxy)-; ~ phenyl]-3-difluoromethyl-4,5-dihydro-4-methyl 1,2,4-triazol-S-(lH)-one (mp 95-97C). ~ ~
Step D 1-(2,4-Dichloro-5-hydroxyphenyl)-3-difluoro-methyl-4,5-dihydro-4-methyl-l,Z,4-triazol-30~ S(lH)-one Hydrolysis of 2.2 g (0.0063 mole~ of l-t2,i-dichloro-., .. i . ~ . . , . . . .. .... .. , .,, . ,. , ... , ~ .. . .
~6~7 5-(1-methylethoxy)phenyl]-3-difluoromethyl-4,5-dihydro-4-methyl-1,2,4-triazol-5(1H)-one in 5 mL of concen-trated sulfuric acid produced 1.4 g of 1-(2,4-di-chloro-5-hydroxyphenyl)-3-difluoromethyl-4,5-dihydro-4-methyl-1,2,4-triazol-5(1H)-one (mp 176-179C).
Step E [2,4-Dichloro-5-(3-difluoromethyl-4,5-dihydro-4-methyl-5-oxo-lH-1,2,4-triazol-1-yl)phenoxy]acetamide In a manner similar to Example 1, the reaction of 0.72 g (0.00023 mole) of 1-(2,4-dichloro-5-hydroxyphenyl)-3-difluromethyl-4,5-dihydro-4-methyl-1,2,4-triazol-5(1H)-one, 0,32 g (0.00023 mole) of potassium carbon-ate, and 0.47 g (0.00025 mole) of iodoacetamide in 5 i mL of acetone produced 0.69 g of [2,4-dichlo~ro-5-(3-:~ 15 difluoromethyl-4,5-dihydro-4-methyl-5-oxo-lH-1,2,4-triazol-l-yl)phenoxy]acetamide (mp 190-193.50Cj.
The nmr spectrum was consistent with the proposed ~'~ structure.
~, The following compounds were prepared~by~the pro-cess of S. Chandrasekaran~et al., Synthetic Communica-tions, 12(9), 727-731 (1982) from Compound A2 and the following reagents.
Compound~ Reagent~
~- B8 ~ tetrahydrofurfuryl alcohol B9 methyl hydroxyacetate B10 ~ 2-methyl-3,3,4,4-tetrafl;uoro-2-butanol Bl2 furfuryl alcohol B13 ~ N,N-dimethylethanolamine B14 ~ 3-hydroxytetrahydrofuran 0 Bl5~ ~ phenol B17 ~ ethanethiol Bl8~ ~ ethyl 2-mercap`toacetate B30 ~trifluoroethanol B31 ~ acetone cya~nohydrin ~ B32 ~benzyl alcohol B33 ~ Z-propanethiol Cll ~ ; O,N-~dimethylhydroxylamine hydrochloride ;~6~ i7 Compound Reagent C12 (2-propynyl)amine C13 aniline C14 dimethylamine Cl5 diethylamine C16 ethylamine hydrochloride C17 glycine methyl ester hydrochloride C22 2-amino-2-methylpropionitrile C23 N-methylaniline Compound B25 was prepared by the method of Lonord et al., J. Or~.. Chem. 27,282-284 (1962) from Compound B23.
Compound A5 was prepared by the hydrolysis of Compound 22 using the procedure described by Kurtev et al., Synthesis tl975), 106-108.
Characterizing properties of some of the com-pounds oE the invention are given in Table 6 below.
~xample 14 N-(2,5-dimethoxyphenylsulfonyl)-2-[2-chloro-4-fluoro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-lH-1,2,4-triazol-1-yl)phenoxy]propionamide Step A~ 2,5-Dimethoxyphenylsulfonamide To a stlrred solution of~ 5~.0 g (0.063 mole) of ;~
2,~5-dimethoxybenzenesulfonyl chloride in 150 mL ~of 25~ ~ tet~rahyd~rofuran was added~dropwlse~80 mL of~ammonia (28% aqueous solution).~ ~Afte~r~complete addition the~
mixture was allowed to stir ~or 1.75 hours at room tempe`rature~ Upon~standing the mi~xture separated into two phases. The~organi~c phase was removed from the 30~ aqueous~phase~and~was~evaporated~under reduced pres-s~ure to~leave~a ~so~lid~ residue. This residue~was~
~ rec~rystalli~zed ~rom hot water~(125 mL) and ethanol s~ (40~mL)~t~o~yield 13.1 g o{ 2,~5-dlmethoxyphenylsulfon-~ ami~de~(mp~ i~46.5-148.5). ~
The nmr spectrum was consistent with the proposed structure.
Step B N-(2,5-Dimethoxyphenylsulfonyl)-2-bromo-propionamide A stirred mixture of 7.0 g tO.032 mole) of 2,5-dime~h-oxyphenylsulfonamide in 10 mL of 2-bromopropionyl chloride was heated at reflux for 40 minutes then allowed to cool to room temperature. The resultant solution was poured into petroleum ether. Crystals formed a~ter scratching the sides of the flask and - we~re collected by filtration. The filter cake was `~ washed four times with fresh petroleum ether to yield 10.3 g of N-(2,5-dimethoxyphenylsulfonyl)-2-bromo-propionamide (mp 116-118C).
The nmr spectrum was consistent with the proposed - ~ structure. ~
Step C N-(2.5-Dimethoxyphenylsulfonyl)-2-[2-chloro-4-fluoro-5-;(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-lH-1,2,4-triazol-l-yl)phenoxy]propionamide To~ a stirred solution of 0.~75 g (0.0026 mole3 of 1-(4-chloro-2-fluoro-5-hydroxyphenyl)-4-difluoro-methyl-4,5-dihyd~o-3-methyl-1,2,4-triazol-5(1H)-one and 0.89 g~(0.0026 mole) of~N-(2~,5-dlmethoxyphenyl-~; su~lfony1)-~2-bro~mop`ropionamide~ in 50 mL~of~ acetone was added~1.04 g (0.0026 mo1e) of potassium carbonate.
After complete addition the mixture was heated~at 45C
for ~two~da~y 5. The~resultant~mixture was cooled and the;solvent was removed by ;evaporation under reduced 3~0~ pressure~to leave a residue~ This ~residue was~dis-solved ln l00 mL~o wate~r~ The aqueous solution was`~
126 ~ 667 acidified by the dropwise addition of concentrated hydrochloric acid producing a precipitate. The preci-pitate was collected by filtration. The filter cake was washed with water and then dried under reduced pressure to leave 1.23 g of N-(2,5-dimethoxyphenylsul-fonyl)-2-[2-chloro-4-fluoro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-lH-1,2,4-triazol-1-yl)phenoxy]-propionamide tmp 168-172C) Compound C90.
The nmr spectrum was consistent with the proposed structure.
Example 15 ~ 1-(4-Chloro-2-fluoro-5-methoxyphenyl)-4,5--~ dihydro-3-methyl-1,2,4-triazol-5(1H)-one as an intermediate ~. . . .
Step A N'-(4-Chloro-2-fluoro-5-methoxyphenyl)-~ acetamidrazone "~ A stirred mixture of 1.91 g (0.01 mole) of 4-chloro-2-fluoro-5-methoxyphenylhydrazine and 1.97 g (0.01 mole) of 3-(1-iminoethylmercapto)-1-propanesulfonic acid, inner salt, (prepared by the method of Reid et al, Ann. Chem. 676, 114 (1964)) in 5~0 mL of anhydrous ~f ethanol was heated at reflux for 1.25 hours. The mix-ture was cooled and evaporated under reduced pressure to leave 3.96 g of a residue. A portion~ of th~is resi-25 ~ due, 3.33~g,~was dissolved in ~50 mL of water. The resultant cloudy solution was~filtered through a pad of celite and the filtrate was~extracted with meth-ylene chloride. The clarlfied~aqueous solution was basified with approximately 8~mL of an aqueous 10%
30~ ~ ~sodium hydroxide solution. An oiI precipitated from he~basic mixture and slowly solidified. This solid :- , ~6~7 was collected by filtration. The filter cake was washed with water to yield 1.31 g of N'-(4-chloro-2-fluoro-5-methoxyphenyl)acetamidrazone (mp 106-107C).
- The nmr analysis was consistent with the proposed structure.
Analysis calc'd -for CgHllClFN30: C 46.66, H 4.79, N 18.14 Found: C 46.10, H 4.81, N 17.70 ,.
Step B 1-(4 Chloro-2-fluoro-S-methoxyphenyl)-4,5-dihydro-3-methyl-1,2,4-triazol-5(lH)-one A solution of 1.71 g (0.0086 mole) of trichloromethyl chloroformate in 5 mL of toluene was added dropwise to a stirred solution of 1.0 g (0.0043 mole) of N'-(4-chloro-2-fluoro-5-methoxyphenyl)acetamidrazone in 50 mL of toluene. After complete addition the mixture was stirred at room temperature for ~ive minutes then was heated slowly until a slow reflux was obtained.
. , Reflux was maintained for approximately 15 minutes.
~ The mixture was cooled and evaporated under reduced pressure to leave 1.22 g of a~ solid. Approximately 1.0 g of this solid was dissolved in 100 mL of methylene chloride. The resultant solution was fil-tered and the filtrate was extracted with three 25 mL
portions of an aqueous 10% sodium~ hydroxide solution followed by three 25 mL portions of lN sodium hydroxide. Each set of three similar extracts were combined and washed with methylene chloride. Both of the washed extracts were acidified with concentrated hydrochloric acid producing a precipitate from each.
The~solids~were collected by fi~ltrat~on to~provide 0.3 g and 0.12 g, from the 10% and lN base solutions respectlvely, of 1-(4-chloro-2-fluoro~-S-methoxy-:
"~ ~ ,, :,, :
.
i7 phenyl)-4,5-dihydro-3-methyl-1,2,4-triazol-5tlH)-one (mp 209-211C).
The nmr spectrum was consistent with the proposed structure.
Example 16 1-(2,4-Dichloro-5-hydroxyphenyl)-3-chloro-di~luoromethyl-4,5-dihydro-4-methyl-1,2,4-triazol-5(1H)-one as an intermediate ~Step A N'-[2,4-Dichloro-5-(1-methylethoxy)phenyl]-;~ lO chlorodi~luoroacetamidrazone :
~ A stirred solution o~ 9.4 g (0.04 mole) of 2,4-di-- ~ chloro-5-(1-methylethoxy)phenylhydrazine in 3S0 mL of absolute methanol was cooled to 0. Gaseous chlorodi-luoroacetonitrile (8.0 g, 0.07;mole) was addéd to the mixture. After complete addition the mixture was ~ allowed to warm to room temperature and stir ~or 3.5 ; ~ hours. The stirring was stopped and the mixture stood at room temperature for two days. The solvent was ~ evaporated from the mixtur~e~under reduced pressure to ;~ 20 leave~13.86 g of N'-~2,4-dichloro-5-(1-methyleth-oxy)phenyl]chlorodifluoroacetamidrazone as an oily residue.
Step B ~ 1-[~2,4-Dichloro-~5-(1-methylethoxy?phenyl]-3-chlorodifluo~romethyl-4,~5-dihydro-i,2,4-25~ triazol-5~1H~-one ~ ;
ln~a manner slmllar to Example I5, Step~B,~the reac-tion~of 13.86~g of``the~oily residue~Erom Step A plus 2.7~g~of~s`i~milar material`prepared in a separate experiment and l9.87 g~(0.1 mo~1e) of trichloromethyl ~6~
chloroEormate in 600 mL of toluene produced 5.4 g of 1-[2,4-dichloro-5-(1-methylethoxy)phenyl]-3-chlorodi-fluoromethyl-4,5-dihydro-1,2,4-triazol-5(1H)-one (mp 115-119C).
The nmr spectrum was consistent with the proposed structure.
Step C 1-[2,4-Dichloro-5-(1 methylethoxy)phenyl]-3-chlorodifluoromethyl-4,5-dihydro-4-methyl-1,2,4-triazol-5(1H)-one In a manner similar to Example 13, Step C, the reaction o~ 4.0 g (0.011 mole) of 1-~2,4-dichloro-5-;~ (l-methylethoxy)phenyl]-3-chlorodifluoromethyl-4,5-di-~; hydro-1,2,4-triazol-5(1H)-one, 4.26 g (0.03 mole) of ;~ methyl iodide, and 2.07 g ~(0.015 mole) of potassium carbonate in 40 mL of aceto~e provided 3.74 g of 1-[2,4-dichloro-5-(1-methylethoxy)phenyl]-3-chlorodi-~luoromethyl-4,5-dihydro-4-methyl-1,2,4-triazol-S(lH)-one as a solid. Recrystallization of a small portion of this solid from ethanol and water provided a pale yellow solid, mp 69-72C.
The nmr spectrum was consistent with the proposed ~; structure.
; Analysis calc'd for O2: C 40-39, H 3.13, N 10.87 Found: C 40.92, H 3.28, N 10.96.
Step~D ~ 1-(2,4-Dichloro-5-hydroxyphenyl)-3-; chlorodifluoromethyl-4,5-dihydro~4-nethyl-1,2,4-~triazol-5(1H)-one ~
I-Iydrolysls oE 2.6 g (0.0067 mole) of 1-[2,4-dlchloro-30 ~ ;5-(1-methylethoxy)phenyl]-3-chlorodifluoromethyl-4,5-i6~6~7 dihydro-4-methyl-1,2,4-triazol-5(1H)-one in 10 mL o~
concentrated sulfuric acid produced 2.17 g of 1-(2,4-dichloro-5-hydroxyphenyl)-3-chlorodifluoromethyl-4,5-dihydro-4-methyl-1,2,4-triazol-5(lH)-one as a solid (mp 146-148C).
The nmr spectrum was consistent with the proposed structure.
Analysis calc'd for CloH6C13F2N3O2: C 3~.86, H 1.76, N 12.20 Found: C 35.30, H 1.59, N lZ.25 HERBICIDAL ACTIVITY
The plant test species used in demonstrating the herbicidal activity of compounds of this invention include cotton (Gossypium hirsutum var. Stoneville), soybean (Glycine max var. Williams), field corn (Zea mays var. Agway 595S), wheat (Triticum aestivium var.
Prodax), rice (Oryza sativa), field bindweed (Convol-vulus arvensis), morningglory (Ipomea lacunosa or Ipomea hederacea, velvetleaf (Abutilon theophrasti), barnyardgrass (Echinochloa crus g~li), green foxtail ~, (Setaria viridis), and johnsongrass (Sorghum hale-~), yellow nutsedge (Cyperus esculentus).
Seeds or tubers of the plant test species were plant~ed in ~urrows in steam sterilized sandy loam soil ~ contained in disposable fiber flats. A topping soil o~ equal porti~ons of sand and sandy loam soil was placed un~iformly on top of each flat to a depth of approximately 0.5 cm.
The flats for the preemergence test were watered, then drenched with the appropriate~amount of a solu-tion of the test compound in a mixture of acetone and .~, :
water containing a small ~amount (up to 0.5% v/v) of sorbitan monolaurate emulsifier/solubilizer. The , :., :
concentration of the test compound in solution was varied to give a range of application rates, generally : ~
,.,,~ ~, ~6~66~
8.0 kg/ha and submultiples thereof. The flats were placed in a greenhouse and watered regularly at the soil surface for 21 days at which time phytotoxicity data were recorded.
The flats for the postemergence test 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 con-taining up to 0.5% sorbitan monolaurate. After spray-ing, the foilage was kept dry for 24 hours, then watered regularly for 21 days, and phytotoxicity data recorded.
Phy~oto~icity data were taken either as percent kill or percent control. Percent control was deter-mined by a method similar to the O 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:
: -, ~
~ :
; ~ ~ ~ .. .. ... .. . .. ... ...
Herbicide Rating System Rating Description Percent of Main Crop Weed Control ~ Description Description.
0 No effect No crop No weed reduction control _ or iniury _ _ __ _ _ - 10 Slight dis- Very poor weed coloration control or stunting Slight Some dis- Poor weed : effect coloration, control stunting or stand loss Crop injury Poor to defi-more pronounced cient weed ~.
but not lasting control _ _ . _ _ _ _ _ .. . ... .... ..
::. 40 Moderate injury, Deficient weed ~: . - crop usually control recovers : 50 ~oderate Crop injury Deficient to effect more lasting, moderate weed recovery control ~.
: : 60 Lasting crop Moderate weed : injury no con~rol recovery _ _ _ : 70 Heavy injury and Control some-~ : stand:loss: : what l:e~ss than :~ : satisfactory : 80 : :Severe Crop nearly des- Satisfactory : troyed:a few to good weed : survivors control 90 ; ~ ~ Only occasional Very good:to live~plants left excetlIlnt 100 Complete Complete crop~ Complete weed effect ~destruction destruction :~;6~ 7 Herbicidal data at selected application rates are given for various compounds of the invention in the tables below. The test compounds are identified in the tables of herbicidal data below by n~mbers which correspond to those used above.
In the Tables of herbicidal data below:
"kg/ha" is kilograms per hectare, "% K" is percent kill, and "~ C" is percent control.
For herbicidal application, the active co~pounds as above defined are formulated into herbicidal com-positions 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, recog-nizing the fact that the formulation and mode of application of a toxicant may a~fect the activity of the material in a given application. Thus, for agricultural use the present herbicidal compounds may be formulated as granules of relatively large particle size, water-soluble or water-dispersible granules, as ' powdery dusts, as wettable powders, as emulsifiable concentrates, as solutions or as any of several other known types of formulations, depending on the desired 25~ mode of application.
For preemergence application these herbicidal composltions are usually applied either as sprays, dusts1 or granuies to the~areas in which suppression of vegetation is desired. For postemergence control of established plant growth, sprays or dusts are most commonly~us;ed. These formulations may contain as lit~tle as 0.5% to as much as 95% or more by weight of active ingredient.
Dusts re free flowing admixture~s of~the active `` 35 ~ ingredient with finely divided solids such as talc, '7 - so -natural clays, kieselguhr, f~ours such as walnut shell and cottonseed flours, and other organic and inorganic solids which act as dispersants and carriers for the toxicant; these finely divided solids have an average particle size of less than about 50 microns. A typi-cal dust formulation useful 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 dispersant. 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 absor-bent, ~readily wet inorganic diluents. Wettable pow-ders 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 ~; wetting, dispersing or emulsifying agent to facilitate dispersion. For example, a useful wettable powder - ~ ~ormulation contains 80.8 parts of the herbicidal -~ compound, 17.9 parts of Palmetto clay, and 1.0 part of sodium lignosulfonate and O.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 facili-tate dispersion on the foliage and absorption by the plant.
~ Other~ useful formulations for herbicidal applica--~ tions are emulsifiable concentrates. Emulsifiable concentrates~are homogeneous liquid or paste composi-tions dispersible in water or other dispersant, and may consist entirely of the herbicidal compound and a : ~ : : :
~.: , : . :. . . ~ : ..
.: ... . .~ ~,. .. : ; --~
i6~'7 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 concen- ~
trates are dispersed in water or other liquid carrier, and normally applied as a spray to the area to be treated. The percentage by weight of the essential - active ingredient may vary according to the manner in which the composition is to be applied, but in general comprises 0.5 to 95% of active ingredient by weight of the herbicidal composition.
Typical wetting, dispersing or emulsifying agents used in agricultural formulations include, for exam-ple, the alkyl and alkylaryl sulfonates and s~lfates and their sodium salts; polyhydric alcohols; and other ~; types of surface active agents, many of which are ; available in commerce. The surface active agent, when used, normally comprises 1% to 15% by weight of the herbicidal composition.
~ Other useful formulations for herbicidal applica-tions include simple solutions of the active ingre-dient in a dispersant in which it is completely solu-ble at the desired concentration, such as acetone, aIkylated naphthalenes, xylene or other organic sol-25~ vents. Granular formulations, wherein the toxicant is carried on~irelatively coarse particles,~are of parti- ;
cular utility for aerial;distribution 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 vapor-i2ation of;a low boiling di~spers;ant solvent carrier,~
such~as~the~Freons, may also be~used. Water-soluble or~water-~di~spersible granules are a3so useful `formula-tions~for herbicidal application of the present com-p-un1s. Su=h granulA- formul~tlons ~r~ tr-e-'l-win~:
~26~6~7 non-dusty, and readily water-soluble or water-misci-ble. The soluble or dispersible granular formulations described in U.S. patent No. 3,920,442, ~ e~
~ ~e~ F~ e~ are useful herein with the pre-sent herbicidal compounds.
The active herbicidal compounds o~ this invention may be formulated and/or applied ~ith insecticides, fungicides, nematicides, plant growth regulators, fertilizers, or other agricultural chemicals and may be used as effective soil sterilants as well as selec-tive herbicides in agriculture. In applying an active ; compound o~ this invention, whether formulated alone or with other agricultural chemicals, an effective amount and concentration of the active compound is of course employed; the amount may be as low as, for example, 7 g/ha or lower.
The active herbicidal compounds of this invention may be used in combination with other herbicides, e.g.
they may be mixed with, say, an equal or lar~er amount o~ a known herbicide such as chloroacetanilide -;~ herbicides such as 2-chloro-N-t2,6-diethylphenyl)-N-(methoxy~ethyl)acetamide (alachlor),;2-chloro-N-(2--` ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl)-acetamide (metolachlor), and N-chloroacetyl-N-(2,6-diethylphenyl)gIycine (diethatyl-ethyl); benzothia-diazinone herbicides such as 3-(1-methylethyl)-(lH) 2,1,3-benzothiadiazin-4-(3H)-one-2,2-dioxide (benta zon); ~triazlne herbicides such as 6-chloro-N-ethyl-N-(l-methylethyl)-1,3,5-triazine-2,4-diamine (atra-;30 zine),; and 2- [4-chloro-6-(ethylamino)-1,3,5-triazin-2-yl]-amino -2-methylpropanenitrile ~cyanazine);
dinitrolaniline herbicid~es such as 2,6-dinitro-N,N-dipropyl-4-(trifluoromethyl)benzeneamine (triflura-lin); and aryl urea herbicides such as N'-(3,4-di-~ : :
:~2~6~7 - ~3 -chlorophenyl)-N,N-dimethylurea (diuron) and N,N-dimethyl-N'-[3-(trifluoromethyl)phenyl]urea (fluo-meturon).
It is apparent that various modifications may be made in the formulation and application of the com-: pounds of this invention, without departing from the inventive concepts herein, as defined in the following claims.
.
,:
.,:
:
.~:
i6ç~7 TABLE_l Percent Control Pre-Emergent Post-Emer~ent PLANT A B A B
Cotton 50 0 90 40 Soybean 10 0 0 10 Corn 0 Rice 50 20 40 0 Wheat 30 0 40 20 Field Bindweed 60 0 40: 0 Morningglory 20 0 60 10 Velvetlea~ 100 0 100 0 Barnyardgrass 70 0 90 . 0 Green foxtail 100 70 90 ~ ~ 0 Johnsongrass 40 0 10 : 0 Yellow nutsedge 30 0 10 0 3 o o 8 owmd ~
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i67 Identifyin~ Proper-~:es Cmpd. Melting Elemental Analysis No. Point (C) E mpincal For ula C H N
111.5-113.5 Cl3Hli C12F2N3 4 NMR ~(CDC13): 2.45 (s,3H), 3.80 (s,3H), 4.70 (s,2H), 6.90 (s,lH), 7.00 (t,lH,J-58 H z), 7.50 (s,l Hl 2 Oil C14H13Cl2F2h304 NM R ~ (CD C13): 1.70 (d,3H,J=7Hz), 2.50 (s,3H), 3.80(s,3H), 4.80(q,1H,J=7Hz), 7.00 (s,lH3, 7.10 (t,lH,J=58Hz), 7.60 (s,lH).
3 Oil Cl4Hl3clF3N304 N MR ~(CD C13): 1.70 (d,3H,J=7Hz), 2.S0 ;; (s,3H), 3.80 (s,3H), 4.80 (q,lH,J=7Hz), 7.00 (t,lH,J=58Hz), 7.00-7.40 (m,2H).
4 Oil ClsHl6clF2N304 NMR ~(CD C13): 1.65 (d,3H,J=7Hz), 2.30 (s,3H), 2.50 (sj 3H), 3.80 (s,3H), 4.80 (q,lH,J=7Hz), 6.80 (s,1H), 7.10 (t,1H,J=
58Uz), 7.~40 (s,lH).
S Oi C l s Hl 5 cl2F 2N 30 4 : NMR ~(CDC13): 1.20(t,3H,J~7Hz), 1 70 (d,3H,J37Hz), 2.50 (s,3H), 4.20 (q,2H,J=
7Hz), 4.70 tq.lH,J~7Hz), h95 (s,lH), 7.05 (t,lH,J=58}1z), 7.60 (s,lH).
;6 Oil~ ClsHlsCIF3N~3O j NMR ô ~C~D C13): 1.~20 (t,3H,J=7Hz), l 70 (d,3H,J=7Hz), 2.50 (s,3H), 4.20 (q,2H,J=
7Hz), 4.70~(q,1H,J=7Hz), 7.00 (t~1H,J=
58 Hz), 7.00-7.40 (m ,~2H).~
7~7 TABLE 6 (Continued) C m pd. M elting ~e m ental Analysis No. Point (C) Empiiical Form~a C H N
.. _ 7 Oil C16Hl8clF2N3O4 NMRô (CDCl3): 1.20 (t,3H,J=7Hz), 1.60 (d,3H,J~7Hz), 2.30 (s,3H), 2.50 (s,3H), 4~25 (q,2H,J=7Hz), 4.70 (q,lH,J=7Hz), 6.80 (s,lH), 7.05 (t,lH,J=58Hz), 7.30 (s,lH).
8 Oil ClsHlsBr2F2N3O4 NMR ~ (CDC13): 1.20 (t,3H,J=7Hz), 1.70 (d,3H,J=7Hz), 2.45 (s,3H), 4.15 (q,2H,J=
7Hz), A80 (q,lH,J=7Hz), 6.95 (s,lH), 7.10 (t,lH,J=58Hz), 7.95 (s,lH).
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i67 Identifyin~ Proper-~:es Cmpd. Melting Elemental Analysis No. Point (C) E mpincal For ula C H N
111.5-113.5 Cl3Hli C12F2N3 4 NMR ~(CDC13): 2.45 (s,3H), 3.80 (s,3H), 4.70 (s,2H), 6.90 (s,lH), 7.00 (t,lH,J-58 H z), 7.50 (s,l Hl 2 Oil C14H13Cl2F2h304 NM R ~ (CD C13): 1.70 (d,3H,J=7Hz), 2.50 (s,3H), 3.80(s,3H), 4.80(q,1H,J=7Hz), 7.00 (s,lH3, 7.10 (t,lH,J=58Hz), 7.60 (s,lH).
3 Oil Cl4Hl3clF3N304 N MR ~(CD C13): 1.70 (d,3H,J=7Hz), 2.S0 ;; (s,3H), 3.80 (s,3H), 4.80 (q,lH,J=7Hz), 7.00 (t,lH,J=58Hz), 7.00-7.40 (m,2H).
4 Oil ClsHl6clF2N304 NMR ~(CD C13): 1.65 (d,3H,J=7Hz), 2.30 (s,3H), 2.50 (sj 3H), 3.80 (s,3H), 4.80 (q,lH,J=7Hz), 6.80 (s,1H), 7.10 (t,1H,J=
58Uz), 7.~40 (s,lH).
S Oi C l s Hl 5 cl2F 2N 30 4 : NMR ~(CDC13): 1.20(t,3H,J~7Hz), 1 70 (d,3H,J37Hz), 2.50 (s,3H), 4.20 (q,2H,J=
7Hz), 4.70 tq.lH,J~7Hz), h95 (s,lH), 7.05 (t,lH,J=58}1z), 7.60 (s,lH).
;6 Oil~ ClsHlsCIF3N~3O j NMR ô ~C~D C13): 1.~20 (t,3H,J=7Hz), l 70 (d,3H,J=7Hz), 2.50 (s,3H), 4.20 (q,2H,J=
7Hz), 4.70~(q,1H,J=7Hz), 7.00 (t~1H,J=
58 Hz), 7.00-7.40 (m ,~2H).~
7~7 TABLE 6 (Continued) C m pd. M elting ~e m ental Analysis No. Point (C) Empiiical Form~a C H N
.. _ 7 Oil C16Hl8clF2N3O4 NMRô (CDCl3): 1.20 (t,3H,J=7Hz), 1.60 (d,3H,J~7Hz), 2.30 (s,3H), 2.50 (s,3H), 4~25 (q,2H,J=7Hz), 4.70 (q,lH,J=7Hz), 6.80 (s,lH), 7.05 (t,lH,J=58Hz), 7.30 (s,lH).
8 Oil ClsHlsBr2F2N3O4 NMR ~ (CDC13): 1.20 (t,3H,J=7Hz), 1.70 (d,3H,J=7Hz), 2.45 (s,3H), 4.15 (q,2H,J=
7Hz), A80 (q,lH,J=7Hz), 6.95 (s,lH), 7.10 (t,lH,J=58Hz), 7.95 (s,lH).
9 83-88 C16Hl7cl2F2N3O4 NMR~(CDCl3): 0.90(t,3H,J=7Hz),1.20-1.90(m,5H), 2.50(s,3H), 4.20(t,2H,J=
7Hz), 4.80 (q,lH,J=7Hæ), 7.00 (s,lH), .lo (t,lH,J=58Hz), 7.60 (s,lH).
7Hz), 4.80 (q,lH,J=7Hæ), 7.00 (s,lH), .lo (t,lH,J=58Hz), 7.60 (s,lH).
10 Oil C16Hl7cl2F2N304 NMR~ (CDCl3): 1.20 (m,6H), 1.70 (d,3H, J=7Hz), 2.50 (s,3H), 4.60-5.30 ~ m ,2H), 6.90 (s,l H), 7.10 (t,l H,J=58 Hz), 7.60 (s,1 H).
11 Oil C17HlgCl2F2N304 N M R ~ (C D C13): 0.70-1.70 (m ,7H), 1.60 (d,3H,J=7Hz), 2.45 (s,3H), 4.15 (t,2H, J=7Hz)j 4.70 (q71H,J=7Hz), 6.95 (s,lH3, 7.05 (t,l H,J=58Hz), 7.60 (s,1H).
12 Oil C 17Hl 9 cl2F 2N 3O 4 NMR~ (CDC13): 0.70-1.80(m,11H), 2.50 (s,3H), A 40-5.30 (m ,2 H), 7. Q0 (s,l H) 7.10 (t,1H,J-58Hz), 7.60 (s,lHl
13 Oil C15H16C12FN304 C 45.94 4.11 10.71 F 46.62 4.16 12.10 N M R ~ ( C D C13): 1.20 (t,3H,J=7Hz), 1.60 (d73H,J 7Hz), 2.35 (s,3H), 4.20 (q,2H,J=
7Hz), 4.75 (q,lH,J=7Hz), 5.75 (d,2H,J=53Hz), 7.00 (s,lH), 7.60 (s,lH).
~ , -: ' :
:, . . . ,, . . . ~ .
~26~7 TABLE 6 (Continued) C m pd. M elting Ele m ental Analysis No~ Poin~(C) Empiric~l Formula C H N
7Hz), 4.75 (q,lH,J=7Hz), 5.75 (d,2H,J=53Hz), 7.00 (s,lH), 7.60 (s,lH).
~ , -: ' :
:, . . . ,, . . . ~ .
~26~7 TABLE 6 (Continued) C m pd. M elting Ele m ental Analysis No~ Poin~(C) Empiric~l Formula C H N
14 110-111 C13HllClF3N304 Oil C16Hl7clF2N304 16 Oil. C16H17ClF3N304 17 118-119 C14Hl3cl2F2N304 C 42.44 3.31 lQ61 F42.60 3.58 10.53 18 0;1 C16Hl7cl2F2N304 C 45.30 4.04 9.90 F44.95 3.79 9.70 19 Oil C17HlgclF3N304 Oil C16H17ClF3N304 C47.13 4.20 10.30 F47.39 4.38 10.35 21 Oil C16H~7cl2F2N30 4 22 137-138 Cl6Hl7clF3N3o4 C47.13 4.20 10.30 F47.23 3.9~ 9.96 52 Oil C17HlgCIF3N304 Al 55-56 C13HllC12F2N304 NMR ~(CDC13): 1.70~d,3H,J~7Hz), 2.SO (s,3H), 4.80 (aOlH,J=7Hz), 7.00 (s,lH), 7.10 (t,lH,J=
58Hz), 7.48 (s,lH), 7.50 (s,lH).
A2 50-55 Cl3HllclF3N3o4 NMR ~ (CD C13j: 1.70 (m,3H), 4.80 (m,1H), 2.40 (s,3H), 7.10-7.50 (m,3H), 8.00 (bs,lH) A3 S6-60 C14H14ClF2N304 N M R ô ( C D C13): 1.60 (d,3H,J=7Hz), 2.30 (s,3H), 2.50 (s,3H~, 4.70 (q,lH~J=7Hz), 6.80 (2,1H), 7.00 (t,1H,J=58Hz), 7.30 ts,1H), 8.30 (s,1H).
A4 Solid ~ ~ C 13HloClF3N 3NaO 4 A5 130-132C12HgClF3N304 H20 C 38.99 3.00 11.37 F 38.95 2.91 11.23 A6 ~ 70-75 C 16H 20 c lF 3N 4o 4 ~6~i~67 TAB L E 6 ( C ontinued) C mpd. Melting Ele m ental Analysis No. Point (C) E mpincal Form~a C H N
Bl Oil C16H16C12F2N406 - N M R~ ( C D C13): 1.40-1.80 (m ,6H), 2.50 (s,3H), 4.40-5.00 (m,4H), 7.00 (s,lH), 7.10 (t,lH,J~
581iz), 7.60 (s,lH).
B2 Oil C16H15Cl2F2N304 C 45.52 3.58 9.95 F 45.24 3.46 9.87 NMRô (CDC13): 1.70 (d,3H,J=7Hz), 2.50 (s,3H), 4.60-5.00 (m,3H), 5.10-5.40 (m,2H), 5.50-6.20 (m,lH), 7.00 (s,lH), 7.10 (t,lH,J=58Hz), 7.60 (s,lH).
B3 Oil C16Hl3cl2F2N304 NMR~(CDC13): 1.70(d,3H,J-7Hz), 2.50(bs,4H), 4.60-A90 (m,3H), 6.95 (s,lH), 7.05 (t,lH,J ~58Hz), 7.60 (s,lH).
B4 Oil C}6H13ClF3N304 C 47.60 3.24 10.41 F 47.88 3.31 9.68 NMR~ (CDC13): 1.65 (d,3H,J=7Hz), 2.45 (m,4H), 4.70(m,3H), 7.05~(t,1H,J-58Hz), 7.10-7.40 (m,2H) B 5 Solid C 16H17Cl2F 2N 30 5 B6 Oil C17H15ClF3N304 C 48.87 3.62 10.06 F 46.60 3.19 10.01 B7 0 C18Hl7ClF3N3o4 C 50.07 3.97 9.73 F 49.68 3.75 9.40 ~ : `
B8 OiI ~ ClgHlgclF3N305 C 48.06 4.26 9.34 F 48.31 3.77 9.00 B 9 Oil ~ C 16 HI s ClF 3N 30 BIO~ Oil ~ C 18Hl 7clF7N 30 4 s~ ail ClSH12ClF3N404 Bl2 ~ 0il ~ ClgHlsclF3N30s B 13 ~ ~ Oil ~ ~ ~ C 17 H 20 ClF 3N 40 4 .. .. . .. ..
6~
TABLE 6 (Continued) C m pd. M elting Ele m ental Analysis No. Point (C) Empirical Formula C H N
.
Bl 4 Oil C 1 7H1 7 ClF 3N 3O 5 B15 Oil ClgHl5clF3N3O4 C51.66 3.42 9.51 F52.15 3.43 9.49 BI6 Solid Cl7Hl5clF3N3O6 C45.40 3.36 9.34 F45.00 3.25 8.90 B17 Oil Cl5HlsclF3M3o3s B18 O;l C17Hl7clF3N3O5s C43.64 3.66 8.98 F43.50 3.73 7.99 Bl9 Oil C14H12C12F3N3O4 NMR~ tCDC13): 1.40 (t,3H,J=7Hz), 2.50 (s,3H), 4.45 (q,2H,J=7Hz), 5.95 (d,lH,J=58Hz), 7.40 (s,lH), 7.50 (t,lH,J=58Hz), 7.65 (s,lH).
B21 131-136 ClgH22clF3N4os B22 Oil ClsH15ClF3N3O5 B23 Oil ClsH15ClF3N3O4S
B25 Solid ClsHlsclF3N3o6s C39.36 3.30 9.18 F39.25 3.00 9.22 B30 Oil ClsHl2clF6N3O4 B31 Oil C17Hl6clF3N4O4 :
B32 Oil C20Hl7clF3N3o4 B33 Oil ~ C16H17ClF3N3O3S
B50 Oil ~ C20Hl7clF3N3o4s B57 Oil Cl7Hl7clF3N3o6 C45.19 3.79 9.30 F45.68 3.77 8.22 Cl 209-210 ~ C12HloCl2F2N4O3 NMR~ CD C13/D MSO ~ d6): 2.20 (s,3H), 4.60 (s,2H), 7.30 (bs,3H), 7.40 (5,1H,J=58Hz), 7.65 (s,1H).
, ~ :
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TABLE 6 (Continued) C m pd. M elting Ele m ental Analysis No. Point (C) Em~ilic Form-da C H N
C 2 Oil.C 14Hl 4 ClF 3N 40 3 N M R ~ ( C D C13): 1.60 (d,3H,J-7Hz), 2.50 (s,3H), 2.90 (d,3H,J=7Hz), 4.75 (q,lH,J=7Hz), 6.80 (bs,lH), 7.10 (t,lH,J=58Hz), 7.20-7.45 (m,2H).
C3 185-188C14H14C12F2N4O5S C 36.61 3.07 12.20 F 36.79 3.01 12.41 NMR~ (CDC13): 1.70 (d,3H,J=7Hz), 2.50 (s,3H), 3.40 (s,3H), A80 (q,lH,J=7Hz), 7.10 (s,lH), 7.10 (t,lH,J=58Hz), 7.70 (s,lH).
C4 OilC14HllC12F5N4O5S C 32.76 2.16 lQ92 F 32.80 2.05 8.77 NMR~ (CDC13): 1.70 ~d,3H,J=7Hz), 2.50 (s,3H), 7 60 ~1HHjJ875Hoz~ 7ilHO)(s,lH), 7.10 k,lH,J=58Hz), . , , . :.
C5 132-135 C13Hl2cl2F2N4O3 C 6 142 -144 C 14 H14 Ci2 F 2 N 40 3 C7 173-175 C12HloclF3N4o3 C8 105-110 C16Hl8clF3N4O3 C9 Oil C17H20ClF3N403 C10 Solid;~ C2oHl8clF3N4o5s C 46.29 3.50 10.80 F 46.77 4.12 ~ 11.03 ClI Oi1 ClsHl6clF3N4O4 C 44.07 3.94 13.71 F 38.44 3.67 11.28 C12 Solid~ C16Hl4clF3N4O3 ~ C 47.71 3.50 13.91 F 46.03 3.60 13.91 C13 57 ~ C19~16CIF3N~43 C 51.77 3.66 12.71 F ~50.90 4.00 11.88 C1~4~ ~Oil ~ ClsH16CIF3N43 ;
C15 ~Solid ; C17H20ClF3N 40 C16~ Oil ClsHl6clF3N403 6~;~
TABLE6 (Con~nued) Cmpd. Melting E~emental Analysis No. Point(C) Empincal Form~a C H N
C17 So~d Cl6Hl6clF3N4os C18 145-150 C14Hl4clF3N4O5s Cl9 Solid C14H14C1~3N4NaO5S
C20 So~d C2oHl7clF3N4Nao5s C21 Oil C18Hl8clF3N4O3 C 50.18 4.21 13.00 F 50.95 3.91 12.38 C22 Oil Cl7Hl7clF3Nso3 C23 O~ C20Hl8clF3N4o3 C25 So~d Cl9H15C12F3N45S C 42.31 2.80 10.39 F 40.44 2.91 8.S6 C2~ 142-143 C13Hl2clF3N4O3 C32 127-134 ClgH16ClF3N4O5S
C38 47-54 C17Hl8clF3N4O3 C 48.75 4.33 13.38 F 47.06 3.73 12.36 C42 O~ C21HlgclF3N4O5s C43 162-166 Cl9H15C12F3N45S
C59 100-105 C2lHlgclF3N4o7s C 44.81 3.40 9.95 F 42.20 2.81 9~61 :
C69 SoW ClgHl6clF3N4O5s C 45.20 3.19 11.10 F 44.74 3.55 10.59 C70~ 208-208.5 ~ C18H13Cl2F3N45S C 41.16 2.49 10.67 F 44.11 3.08 10.96 C71 ~ So~d~ ~ Clg~14C12F3N4 5SNa C72 ~135-i40 C20H18ClF3N4O5S
C73~So~d ClgH15Cl2F3N4O5s C74 110 ClgH15ClF3N507S
'' : `, : I . :
Q.~ 7 TABLE 6 (Continued) Cmpd. ~lelting Elemental Analy~s No. Point ~C) Empirical Formula C H N
C75 175-180 ClgH14C13F3N405s C76 171-173 Cl9H15C13F2N45S
C77 66-70 ClgHlsClF4N405S
C78 248-Z53 C22H22ClF3N4o5s C79 Solid C21H20ClF3N4O5S
C80 67-70 C20HlsClF6N40 5S
C81 58-62 C20Hl8clF3N4o6s C82 Solid C20HlgClF3N4O5S
C83 108-113 C20H17ClF3N46SNa C84 155-157 C20H17C12F3N45S C43.413.1010.13 F42.653.309.I9 ~ . ., C85 69-74 C17Hl4clF3N4O5s2 ,::
~-; C86 Solid ClgH20clF3N4o5 ,.
C87 Solid C23H24ClF3N405s C49.244.319.99 F46.404.218.63 C88 Solid ~ ClgHl7C12FN405S
C89 So~id C18H18ClF3N 4O5 C90 168-172 C21H20ClF3N407S
C91 Solid C21HlgClF3N~407SNa C9Z~ Sohd ~ C20H17ClF3N40sSNa C93 ~173-179 C21HlgclF3N407s C94 65-70~ Cl9H15C12F3N45S
C95 110 ~ ClgHlsBrC1~3N4OsS C 39.092.59 9.60 F38.752.669.64 C97 ~ Solid ~ C2oH22clF3N4os TABL E 6 ( Continued) Cmpd. Melting Element~l Analy~is No. Point (C) Empirical Formula C H N
C98 Solid C 21H17ClF3N qO 7SNa C 99 Solid C 20H1 7BrClF 3N 40 6S
C100 Solid C2oHl6BrclF3N4o6sNa C101 Solid C20HlsClF3N505s C45.33 2.85 13.22 F44.83 2.42 13.06 C102 60-70 C18Hl8clF3N405s C43~69 3.67 11.32 F43.2q 4.01 10.71 Cl03 80-95 Cl~Hl8clF3N407s Cl04 Oil C21H2qclF3N4O5 C 105 Solid C 21 H 20 ClF 3N 4O 7S
Cl06 Solid C21HlgClF3N407SNa C107 170 Cl9HlsClF3l~l5075 C108 Solid C l gHl gClF 3N 50 4 ClO9 01l C22H22ClF3N406S
Cll0 85-90 C2zH21ClF3N406SNa Clll Oil ClgHl6clF3N406s C112 174-176 C20H18ClF3N407S
C113 Oil ~ ~ C20H17C12P3N405S
C114 60-70 ~ C20H16C12F3N405SNa ~:."
C115 ~Solid~ ClgHl sBrClF3N 40 sS
C116 ~ 188-191 C20H16ClF3N47 Cl17 ~ >230 C23HlgClF3NqOss c11~8 ~ 144-147~ C21HIgCl3F2N4o7s Cll9 ~ 211-212 ~ C20H18CIF3N407S
~ ~ , ~ . , . . . :. , , "
- 105 ~
TABLE 6 (Continued) C m pd. M elting Ele m ental Analysis No. Point (~C) Empincal Form~a C H N
C120 Solid C2oHl7clF3N4o7sNa C121 Solid C20Hl7ClF3N4O7SNa C122 105-110 C2lH2ocl2F2N4o7s C123 163-166 C21H2OBrF3N4SO7 C124 Solid CzlH21ClF3N5O5S
C125 Solid C20Hl5clF6N4o6s C126 Solid C 20H17ClF3N 5O 7s C127 Solid C2gH34ClF3N4F3O5s C128 Solid C2gH33ClF3N4OsSNa : .
C129 147-149 C19H16C1F3N4O6S C 43.81 3.10 10.76 : . : . F44.31 3.26 10.54 ,~ . . . . .
C130 Solid ClgHlsClF3N 4O 6SNa C131 198-20I C23H22C1F3N4O6S C 48.05 3.86 9.74 F 47.11 3.89 9.34 C132 Solid C20H14C1F6N4O6SNa C133 Solid C2OH15BrF6N4O6S
C136 Solid C21H20C1F3N406S
CI38 136-140 ~ C23HIaCIF3N4O55 C139 Solid ~ C21H19CIF3N4O6SNa 0833W30080W md ~ ~
i6~
- 10~ -Table_7 P_eemergence Herbicidal Activity Compound No.1 2 3 4 - Rate (kg/ha) 2.0 4.b ~ r---%K %C %K %C %K ~ %K %C
Species , Cotton 100 100 10050 Soybean 0 90 30 0 Field Corn 80 100 10030 Rice 50 100 90 30 Wheat 0 100 10030 Field Bindweed100 100 100100 Morningglory 100 100 60 0 Velvetleaf 100 100 ND100 Barnyardgrass 90 100 100100 Green Foxtail100 100 100ND
Johnsongrass 80 100 10095 Yellow Nutsedge70 100 100 0 ~, ' , .
Compound No. _ 6 7 _ 8 9 Rate (kg/ha) 2.:0 2.02.0 ~ 2.0 ~
~R~ %K %C %K %C %~ %c Species _ --Cotton 100 60 70 100 Soybean 10 30 20 20 Field Corn 70 30 20 80 Rice 80 50 60 90 Wheat 100 80 40 90 Field:Bindweed 100 60 80 100 Morningglory 100 ~ 70 90 100 Velvetleaf :: 100 100 100 100 Barnyardgrass 100 100 100 100 Green Foxtail 100 100 100 100 Johnsongrass ~ 90 90 90 100 Yellow Nutsedge 10-0 ~50 80 100 Table 7 (Cont.) Preemer~e~ rrbicidal Activity Compound No.10 11 12 13 Rate (kg/ha)2.0 2.0 2.0 2.0 ~K~ %C ~R~ R~ 'n~---SDecies ~ ~
Cotton 100 40 100 30 Soybean 20 lO0 30 20 - Field Corn100 40 20 20 Rice 90 90 70 10 Wheat 90 70 50 .10 Pield Bindweed 100 100 90 20 Morningglory100 100 100 50 Velvetleaf100 100 100 80 Barnyardgrass 100 100 lO0 40 Green Foxtail 100 100 100 40 Johnsongrass100 100 90 40 Yellow Nutsedge 100 90 90 lO
. ' .
.
Compound No. 14 15 16 17 ~ :: Rate (kg/ha) 1.0 1.0 1.0 ~ r---:~- %~ %C ~R~ %K %C %K %C
~ Species ;
~:: Cotton 90 100 lO0 100 ~-~ Soybean 0 40 30 0 ~:: Field Corn 60 40 100 30 :~ Rice 30 80 90 30 - : : : Wheat 20 100lO0lO
` Field Bindweed lO0 90 100 90 : Morningglory 90 100 90 90 Velvetleaf 100 100 100 90 Barnyardgrass::50 : 100 100 90 Green Foxtail 10 100 lO0 lO
Johnsongrass 60 : : 90 90 80 :; Yellow Nutsedge ~ 100 90 lO0 60 ::;: ~ , Table 7 (Cont.~
Preemer~ence Herbicidal Activity Compound No. 18 19 20 21 Rate (kg/ha) 0.5 2.0 0.5 2.0 ~ %K %C %K %C ~ n~--Species Cotton ` 10 80 30 80 Soybean 20 100 0 20 Field Corn lO 80 0 80 Rice 0 90 20 30 Wheat 0 50 0 o Field Bindweed 0 lO0 . 90 lO0 Morningglory 0 90 90 90 Velvetleaf 30 lO0 lO0 lO0 Barnyardgrass 0 100 50 100 Green Foxtail 90 lO0 lO0 100 Johnsongrass 0 90 30 90 Yellow Nutsedge 0 lO0 lO 70 . . :
Compound No. 51 . 52 .
Rate (kg/ha) 2.0 2.0 : %K ~C %K %C
Species: _ _ :
Cotton : 70 : 100 Soybean lO : 70 Field Corn . 30 100 Rice ~ 40 ~ 95 Wheat 0 : 100 ~ :
Field Bindweed 90 lO0 Morningglory 80 ~ 95 ;Velvetlea~ : :lO0: 100 ~ :
Barnyardgrass 30: 100 Green ~oxt:ail : 20 lO0 Johnsongrass : 80 100 Yellow Nutsedge: 40 100 6~7 Table 7 (Cont.) Preemergence Herbicidal Activity Compound No. Al' A2 A3 Rate (kg/ha) 4.0 2.0 2.0 ~ %K ~%C %K %C
Species Cotton 100 10 80 Soybean 0 0 20 Field Corn 0 0 Rice 80 10 70 Wheat 80 20 100 Field Bindweed 100 30 50 Morningglory . 100 10 0 Velvetleaf 100 ND 100 Barnyardgrass 100 40 100 Green Foxtail 100 100 ND
Johnsongrass 80 30 95 Yellow Nutsedge 90 20 0 :
~: Compound No. A4 ~A6 Bl B2 Rate:(kg/ha) . 1.0 0 5 2.0 2.0 ~ %K %C %K %C %K %C_ : ~:: ` Spec es :.~
~- Cotton 90 80 100 100 ~: Soybean 10 30 10 10 : Field Corn 40 30 30 90 ~ Rice 80 30 90 90 : Wheat 80: 30 70 90 : : ~ Field ~indweed 70 70 I00 100 Morningglory~ 90 90 100 100 Velvetleaf 100 90 100 100 : ~ Barnyardgrass 100 100 100 100 Green Foxtail 100 : 100 100 100 :Johnsongrass 90 : 80 90 100 : Yellow Nutsedge 90 80 100 100 ; ~ , . , . . , . ~ . .. ..
: ,~: . : . . .. .
~6~7 Table 7 (Cont.) Preemergence Herbicidal Activity Compound No. B3 B4 _ B5 B6 Rate (kg/ha) 2.0- . 1.0 2.0 1.0 %K %C %R %C %K %C %~ %C
Species Cotton 100 90 100 100 Soybean 0 40 20 10 Field Corn 30 80 50 40 Rice 70 80 90 90 Wheat 80 90 90 90 Field Bindweed 90 100 100 90 Morningglory 100 90 90 100 Velvetleaf 100 100 100 100 Barnyardgrass 100 100 100 100 Green Foxtail 100 100 100 100 Johnsongrass 100 90 100 90 Yellow Nutsedge 100 90 100 100 Compound No. B7 B8 B9 B10 Rate (kg/ha) 1.02.0 0.5 1.0 ~
%K ~C ~ ~C %K ~C %K %C
Species Cotton 100 100 100 20 Soybean 30 50 20 0 Field Corn 80 100 30 30 Rice 90 90 60 30 Wheat 80 90 40 70 Field Bindweed: lQ0 100 80 100 Morningglory 100 100 60 90 :Velvetleaf 100 : 100 100 100 Barnrardgrass 100 ~~ 100 100 100 Green Foxtail ~ .100 100 :100 100 Johnsongrass~: : : 80:: 100 50 :80 Yel;low Nutsedge100;100 ~ : 10~0 70 6~:i7 Table 7 ~Cont ) Preemergence Herbicidal Activity Compound No.Bll B12 B13 B14 Rate (kg/ha)1.0 l.0 1 0 1 0 Species ~r~ T~ %~ ~C ~----R~ ~K ' ~C
Cotton 100 lO0 90 100 Soybean 10 10 100 20 Field Corn 60 20 90 40 Rice 60 60 90 80 Wheat 90 50 90 go Field Bindweed 100 70 100 90 Morningglory 90 90 100 lO0 Velvetleaf lO0 lO0 100 100 Barnyardgrass 100 100 100 100 Green Foxtail 100 100 100 100 Johnsongrass 90 80 90 90 Yellow Nutsedge 100 90 90 90 , Compound No. B15 B16 : B17 B18 Rate (kg/ha): ~2.0 I.0 -- I.0 -- 2.-0 S e~ies ~~ %C %K %C: %K %C ~%~ %C
~ : : P -- -- . .
Cotton 100 80 ::100 100 Soybean 70 : 20 40 : 30 Field Corn 90 60 80 60 Rice ~ 90 :60 80 80 Wheat 90 50 90 90 Field Bindweed 100 :90 80 100 Morningglory 100 100 100 100 VelvetIeaf :: 100::: :: 100 100 : 100 Barnyardgrass 100 : 100 100 100 :Green::Foxtail :10:0:: 100 : 90: 100 Johnson`grass:~ 100 ~90 :90 90 Yel~low:Nutsedge 100 ~ 100 :100 100 ~: ~ . ~ .. . .
. . ~ .
Table 7 (Cont.) Preemergence Herbicidal Activity Compound No. B21 B22 B23 B25 Rate (kg/ha) 1.0 0.5 1.0 _1.0 %K %C %K _ %C %X %C %X %C
SDecies Cotton 90 60 70 70 Soybean 0 0 0 50 Field Corn 50 0 30 70 Rice 40 40 80 60 Wheat 50 10 60 50 Field Bindweed 90 20 90 70 Morningglory 90 40 100 100 Velvetleaf 100 100 100 100 Barnyardgrass 100 ~0 90 100 Green Foxtail 90 80 100 100 Johnsongrass 40 20 70 90 Yellow Nutsedge 90 90 80 90 .
: . Compound No. B30 _ B31_ B32 B3~3 Rate (kg/ha) 0.5 1.00. 5 1~ 0 %K ~ %C %K%C %K%C %X%C
SDecies : Cotton 100 100 20 : 80 ~ Soybean 0 10 : 0 40 :~:: Field Corn 10 :20 20 90 Rice : 20: 50 20 90 Wheat 20 30 10 60 Field Bindweed 20 70 30 90 Morningglory :50 80 30 90 - Velvetlea~ 100 100 90: 100 Barnyardgrass 100 100 100 100 : : : Green Foxtail:: : 100: 100 100 100 Johns o ng ra s s ~: ~ 5 0 8 0 S 0 : 7 0 :~2:~ : Yellow Nutsed~ge ~100 :~90 ~ 90 90 ~;~66~
Table 7 (Cont.) Preemergence ~erbicidal Activity Compound No. B50 B57 Rate (kg/ha) 0.5 0.5 %C %K %C
Species Cotton 50 100 Soybean 20 10 Field Corn 30 40 Rice 40 50 Wheat 60 60 Field Bindweed 10 90 Morningglory 50 70 Velvetleaf 100 100 Barnyardgrass 90 100 Green Foxtail 100 100 Johnsongrass 50 70 Yellow Nutsedge 50 90 . .
:~
: . ,Compo~nd No _Ci C2 C3 C4 Rate (kg/haj 2~ 1.0%C ~ F %K2-0%C
; Species ~: Cotton 70 lO0 100 40 ;~ Soybean 40 100 40 0 Field Corn 60 100 80 0 : : Rice : 20 100 80 0 :~ Wheat 20 100 90 40 Field Bindweed 100 100 100 80 ~ : ~Morningglory . 100 100 100 90 :~ Velvetleaf 100 lO0 100 lO0 : Barnyardgrass 80 100 100 90 : Green Foxtail 90 lO0 100 90 . Johnsongrass 80 ~ 100 100 50 :: Yellow~Nutsedge 80 100 100 50 : :~
: : :
. ~ ~
:, ~ , : ' Table 7 (Cont.) Preemergence Herbicidal Activity Compound No. C5 C6 C7 _ C8 Rate (kg/ha) 2.0 2 0~ 1.0- 2.0 %K ~OC %~ ~C %K %C %K %C
Species ____ ___ _ _ _ _ _ Cotton 100 100 100 90 Soybean 100 90 10 100 Field Corn 100 100 100 100 Rice 100 100 40 100 Wheat 100 I00 30 100 Field Bindweed 100 100 100 100 Morningglory 100 90 100 100 Velvetleaf 100 100 100 100 Barnyardgrass 100 100 100 100 Green Foxtail 100 100 90 100 Johnsongrass 100 100 90 100 Yellow Nutsedge 100 100 100 90 .
: . - .
.. Compound No. C9 C10 Cll C12 Rate (kg/ha) 1.0 ~~~ ~~ :1.0 1.0 ~:~ %K %~ %K %C %K %C %K %C
i Species ::~ Cotton 80 100 100 100 : Soybean 90: 90 100 100 ~ Field Corn 100 20 100 100 .- Rice 90 80 100 100 ` : Wheat 100 70 100 100 : : FieId Bindweed 100 ~ 100 100 100 : Morningglory100 100 100 100 : Yelretleaf 100 100 100 100 : Barnyardgrass100 lQ0 100 100 ~:: : Green Foxtail100 :100 ~ 100 100 Johnsongrass100 90 100 100 Yellow Nutsedge 80 ~ 60 100 100 - llS -Table 7 (Cont.) Preemergence Herbicidal Activity Compound No._C13 C14 C15 C16 Rate (kg/ha)2.0 2.0 2.0 2.0 %~ %C %~------%C %R %C %K %C
Species Cotton 100 100 100 100 Soybean 100 100- 100 100 Field Corn 90 100 100 100 Rice 100 100 100 100 Wheat .90 100 100 100 ~ield Bindweed 100 100 100 100 Morningglory 100 100 100 100 :: Velvetleaf 100 100 100 100 Barnyardgrass 100 100 100 100 Green Foxtail 100 100 100 100 Johnsongrass 100 100 100 100 :~ Yellow Nutsedge 100 100 100 100 ~, .
.' :
~ . Compound ~o. C17 C18 Cl9 _ C20 :. Rate (kg/ha) 2.0 1.0 1.0 -r~----%~ %C %~ %C %~ ~C ~1~ %C
~: : Species : _ :
., Cotton 100 100 100 100 Soybean 100 : 0 20 80 Field Corn 100 70 100 50 Rice 90 80 60 : 30 Wheat 90 S0 40 10 Field Bindweed 100;: 80 80: 100 Morningglory~ 100 100 100 100 Velvetleaf~ ~ ~ 100 100 : ::100 1:00 Barnyardgrass: :100 100 100 100 Green Foxtail::: 100 100 100 100 Johnsongrass:~ : 100 90 :90 40 Yeil~ow Nut:se;dge ~100 ~90 ~ 80~ 10 ~: - ~. . :;. ,, ::. :; .
Table 7 (Cont.) Preemergence Herbicidal Activity Compound No. C21 C22 C23 C24 Rate (kg/ha) -r.-o~ . o 1 . o 1 . o ~K %C %K %C ~oK %C %K %C
Species _ _ Cot~on 100 100 30 40 Soybean ga 100 50 10 Field Corn 100 lO0 90 80 Rice 80 100 20 30 Wheat 100 100 70 0 Field Bindweed 100 100 100 90 Morningglory 100 100 100 100 Velvetleaf 100 100 100 90 Barnyardgrass 100 100 100 80 Green Foxtail 100 100 100 100 Johnsongrass 100 100 100 70 Yellow Nutsedge 80 100 40 30 , .
- Compound No. C25 C26 C32 C38 Rate (kg/ha) 2.0 1.0 1.0 1.0 : ~K %C %K ~C %K %C SK- %C
Species _ _ ~ :
: Cotton 100 100 100 90 Soybean 30 100 40 100 : Field Corn 70 100 20 100 ~ : Rice 60 90 50 100 :~. : Wheat 30 100 lO 100 ~`i : Field Bindwee:d ~ 100 100 100 : 100 : : Morningglory 100 100 100 : 100 : Velvetleaf 100 ~100 100 100 : Barnyardgrass 100 100 100 100 : Green Foxtail 90 100 80 100 : : Johnsongrass 70 100 80 100 Yellow Nutsedge 80 100 ~40 ND
Table 7 (Cont.) Preemergence Herbicidal Activit~
Compound No. C42 C43 C59 C69 Rate (kg/ha) 1.0 . i.0 1-0 0.5 %K ~ ~C %K %C %K %C %K %C
SDecies _ Cotton 90 100 100 40 Soybean 70 70 S0 10 Field Corn 40 70 70 30 Rice 60 90 80 30 Wheat 70 70 40 0 Field Bindweed100 100 lO0 90 ~orningglory 100 100 100 80 Velvetleaf 100 100 100 lO0 Barnyardgrass 100 100 100 20 Green Foxtail 100 100 100 20 Johnsongrass 60 95 100 40 Yellow Nutsedge 70 100 70 70 . .
.
Compound No. C70 C71 C72 C73 .
Rate (kg/ha) ---T~ r~~~ 1.0 1.0 %K %C ~ F %X %C %K %C
Species Cotton lO0 100 100 80 Soybean: 20 50 50 30 Field Corn 30 S0 : 60 30 Rice 70: 40 30 40 Wheat : :20 :40 20 ~ 50 FieId Bindweed 100 100 100 100 Morningglory 100 :I00 :100 100 Velvetleaf 100 100 lO0 100 Barnyardgrass 20 90; 100 90 Green Foxtail : 0 40 95 100 Johnsongrass: 80 ~ 60 90 80 Yell~ow Nutsedge 90 4060 20 "~
:: : :,: . ,.. :. . ,. - , , 666~
Table 7 (Cont.) Preemer~ence Herbicidal Activity Compound No. C74 C75 C76 C77 Rate (kg/ha) 1.0 _ l.0 1.0 1.0 %K 30C %~ %C %K ~C %X ~C
S~ecies ~ ~ ~
Cotton 100 90 60 95 Soybean 80 30 30 40 Field Corn 0 50 20 30 Rice 40 60 30 70 Wheat 30 40 20 60 Field Bindweed90 100 100 100 Morningglory 100 .lO0 100 100 Velvetleaf 100 100 100 100 Barnyardgrass 85 95 100 100 Green Foxtail 100 95 70 100 Johnsongrass 70 80 40 95 Yellow Nutsedge 20 30 30 30 Compound No. C78 C79 C80 C81. ~ :
Rate ~kg/ha) 1.0 ~ S-- 1.0~ - : 1 0 ~~~
Species _ %K ~.C %~ ~C ~ R~
Cotton 80 50 60 100 Soybean 40 : 0 20 100 Field Corn 30 10 0 50 Rice~ 50 50 20 50 Wheat ~ 40 20 30 100 Field Bindweed 100 80100: 100 Morningglory 100 100100 100 Velvetleaf 100 100100 100 Barnyardgra:ss : 100 ~ 80 95 100 Green:Foxtail ~ 90 100:100 100 Johnsongrass: 40 80 95 :100 Yellow Nutsedge 30 20 0 80 : :
~6~i~;6~
Table 7 (Cont.) Preemergence Herbicidal Activity Compound No. C82 C83 CB4 C85 Rate (kg/ha) 1.0 1.0 1.0 1.0 %K 7~C %K %C %K %C %K %C
S~ecies . .
Cotton 100 95 10 100 Soybean 10 95 0 30 Field Corn 20 20 10 95 Rice 30 40 20 80 Wheat 20 30 0 80 Field Bindweed 100 10030 100 Morningglory 100 100100 100 Velvetleaf ldO 100 90 100 Barnyardgrass 95 95 10 100 Green Foxtail 100 90 30 100 Johnsongrass 95 80 30 100 Yellow Nutsedge 10 20 ND ND
Compound No. . C86 - C87 C88C89 Rate (kg/ha) ~~~~ . 1.0 1.0 1.0 ~K %C ~R~ %K %C %K ~C
Species :: -Cotton 100 30 0 90 Soybean 70 20 10 30 Field Corn100 10 10 60 Rice 90 40 0 90 Wheat 90: 10 0 80 Field Bindweed 100 100 0 100 Morningglory 100: 100 0 100 Velvetleaf100 100 10 100 Barnyardgrass 100 95 40 100 Green Foxtail 100 0 O 100 Johnsongrass: - 100: : 30 10 95 Yellow Nutsedge ND ND ND ND
,: -: . : - , ... . .
Table 7 (Cont.) Preemergence_Herbicidal Activity Compound No. . C90 _C91 C92 C93 Rate (kg/ha) 1.0 1.0 1.0 1 0 %K %C %K__ ~C %K %C %K %C
Species _ _ _ Cotton 100 100 100 20 Soybean 100 90 30 0 Field Corn 80 80 20 30 Rice 80 90 40 50 Wheat 70 50 30 10 Field Bindweed 100 100 100 80 Morningglory 100 100 100 80 Ve.lvetleaf 100 100 100 100 Barnyardgrass 100 100 100 100 Green Foxtail 100 100 100 0 Johnsongrass 100 95 80 30 Yellow Nutsedge ND ND ND ND
.: .
, :~ Compound No. C94 C95 C97 C98 ~ Rate (kg/ha) 1.0 1.0 . I.0 0.5 :~ %K %C %K%C %K96C %~ ~C
:~' Species _ _ _ Cotton 80 100 100 100 ~' Soybean 20 60 20 30 : Field Corn 20 20 70 40 Rice 20 30 80 20 : Wheat 0: 10 70 20 ~ Field Bindweed 100 100 100 100 :~ : Morningglory 100 100 100 100 Velve~Iea:E 100 100 100 100 Barnyardgrass: 60 40 100~ 90 ~ Green Foxtail 50 50 100 80 : ~ Johnsongrass 60 60 90 95 : ~ Yellow Nutsedge ND ND ND ND
" ~ ~
6~i7 ~ 121 -Table 7 (Cont.) Preemergence Herbicidal Activity Compound No.C99 C100 C101 C102 Rate (kg/ha)0.5 0.5 0.~- 0.5 ~ %~ ~C ~K %C
Species_ Cotton 80 80 95 30 Soybean 70 S0 30 20 Field Corn 30 60 10 50 Rice 20 60 20 80 Wheat 10 20 10 50 Field Bindweed100 100 90 20 Morningglory100 100 100 80 Velvetleaf 100 100 100 100 Barnyardgrass10 70 60 100 Green Foxtail100 80 40 100 Johnsongrass 80 80 50 80 Yellow Nutsedge ND ND ND ND
.
- .
~ompound No. C103 C104_ C105 C106 Rate (kg/ha~ 0.5 0.5 ~ 0.~5 ~: 0.5 %K %C %K %C %~ %C %~ %C
Species ~
Cotton 30 30 100 100 Soybean ~ 10 10 95 ~ 90 Field Corn 30 90 70 30 Rice 50: 80 95 90 Wheat : 30 80 50 30 ~ield Bindweed40 100 100 100 Morningglory60: 90 lO0 100 Velvetl~af 100 100 100 100 Barnyardgrass : 95 95 100 : 100 Gree:n Foxtai~100 ~100 100 100 Johnsongra~s 80 ~ :95 lO0 100 YelIow Nutsedge ND : ::ND ~ ND ND
~266~$7 Table 7 (Cont.) Preemergence Herbicidal Activity Compound No. C107 C108 C109 CllO
Rate (kg/ha) 0.5 0.5 0.5 0.5 ~ F %K %C %~ %C ~oK ~ %C
SDecies Cotton 90 100 70 30 Soybean. 10 95 90 95 Field Corn 20 100 100 100 Rice 40 95 95 90 Wheat . 0 95 100 100 Field Bindweed 80 90. 95 100 Morningglory 95 100 100 100 Velvetleaf 100 100 100 100 Barnyardgrass 40 80 100 100 Green Foxtail 0 100 100 100 Johnsongrass 50 100 100 100 Yellow Nutsedge ND ND ND ND
~ .
: Compound No. Clll C112 C113 . C114 Rate (kg/ha) 0.5 0.5 ~~~-S~~ ~0.5 ~K ~'C %K _~OC %K ~C %K %C
': Species ; Cotton 20 9050 30 Soybean 40 40 0 0 ~ Field Corn 10 010 10 : : Rice 70 2020 . 20 Wheat 50 1010 10 Field:Bindweed 70 100 100 90 ~: Morningglory~ 70 90 90 95 : Velvetleaf 90 : 100 100 100 Barnyardgrass 100 40 50 70 : : Green Foxtail 100 80 30 70 ;~:: : Johnsongrass 70 95 30 70 Yellow Nutsedge :ND ND : ND ND
.. ~ . .: . .. ..... . .
~ - ~ . . : , - . . , ,,;; . . , , . : .. . . .
Table 7 (Cont.) Preemergence Herbicidal Activity CPmpound No. C115 C116 C117 C118 Rate (kg/ha) 0.5 0.5 0.5 0.5 %K _ _ C %X %C %K %C %K_ %C
Species _ _ Cotton 80 9S 50 20 Soybean 30 0 95 0 Field Corn 10 10 10 10 Rice 10 20 30 0 Wheat 30 10 0 10 Field Bindweed . 100 - 90 100 80 Morningglory 100 95 100 50 Velvetleaf 100 100 100 50 Barnyardgrass 50 80 40 10 Green Foxtail 90 40 80 10 Johnsongrass 90 80 20 10 Yellow NutsedgeND ND ND ND
Compound NO.Cll9 . .C120 C121 C122 Rate (kg/ha)~~~~~ O.S ~~0.5 ~ O S
--F~ -%R %C ~X %G ~ %C
Species _ ::
Cotton 50 70 95 70 Soybean 30 20 20 50 Field Corn 10 10 20 40 Rice 30 20 30 0 Wheat 30 10 10 ~10 Field Bindweed100 100 100 100 Morningg:lory100 ~ 90 90 ~ 80 Velve~leaf 100 100 lob loo Barnyardgrass 50 :80 70 70 Green Foxtail 0~ 0 20 50 Johnsongrass 70: 70 90 100 Yellow Nutsedge : ND ND : ND ND
~ :. .:.. - , : :
~26~i66~
Table 7 (Cont.) Preemergence Herbicidal Activity Compound No.C123 C124 C125 Rate (kg/ha)~~~1~ ~ ~ 0.5 0.5 %K _ %C ~ F %K %C
Species Cotton 50 20 20 Soybean S0 60 30 Field Corn 0 70 10 Rice 60 80 10 Wheat 10 60 lO
Field Bindweed 100 100 80 Morningglory 100 95 90 Velvetleaf 100 100 100 Barnyardgrass 100 100 30 Green Fox~ail 10 100 50 Johnsongrass 100 100 10 Yellow Nutsedge ND ND ND
,~
!
' ~,.
, :
': .
~ : 0833W30080Wmd~ ~
. :, ,-, : ~ , --:: -:: : ,~. ~. . .
. ~ .
.
Table 8 Postemergence Herblcidal Activity Compound No. 1 2 3 4 Rate.(kg/ha)_ 2.0 4.0 2.0 2.0 ~oK %C %~ %C %~ %C %X %C
Species _ _ ___ _ __ _ Cotton 100 100 100 90 Soybean 40 0 60 0 Field Corn 90 100 100 0 Rice 80 100 100 ~0 Wheat 10 100 90 90 Field Bindweed 100 100 lO0 100 Morningglory100 100 100 70 VelvetIea~ 100 100 ND 100 Barnyardgrass 100 100 100 90 Green Foxtail 100 100 ND ND
Johnsongrass 90 95 100 70 Yellow Nutsedge 50 50 100 0 Compound No. 6 7 8 9 Rate (kg/ha) 2.0 2.0 2.0 2.0 %~ %~ %K -~0-C %K %C %K %C
Species _ Cotton 100 90 100 100 Soybean 50 40 50 30 Field Corn100 40 30 100 Rice : lO0 : 80 90 70 Wheat 100 90 30 80 Field Bindweed 100 100 100 100 Morningglory 100 80 100 80 Velvetleaf 100 100 100 100 Barnyardgrass 100 100 100 100 Green Foxtail 100 100 100 100 Johnsongrass I00: 100 :70 80 Yellow:Nutsedge 100 :70 :30 80 ~6~i~7 Table 8 (Cont.) Postemergence Herbicidal Activity Compound No. 10 11 12 13 Rate (kg/ha) 2.0 2.0 2.0 2.0 ~oK %C %K %C %~ %C %X %C
Species ~
Cotton 100 100 100 70 Soybean 30 50 30 20 Field Corn 100 60 30 10 Rice 90 90 50 30 Wheat 100 90 70 20 Pield Bindweed 100 100 100 50 Morningglory 30 100 100 80 Velvetleaf 100 100 100 80 Barnyardgrass 90 100 100 80 Green Foxtail 100 100 100 40 Johnsongrass 80 80 90 30 Yellow Nutsedge 90 90 50 20 :
Compound No. 14 15_ 16 17 Rate tkg/ha) 1.0 1.0 ~.~ Z.0 %K %C %K %C %~ %C %~ %C
SDecies Cotton 100 100 100 100 Soybean 60 40 30 70 Field Corn 10 30 10 70 Rice : 30 90 30 30 Wheat 10 60 40 20 Pield Bindweed 100 100 90 90 Morningglory 100 100 100 100 Velvetleaf 100 :100 10'0 100 Barnyardgrass 100 100 100 70 Green Foxtail 90 100 100 20 Johnsongrass 80 90 80 70 Yellow Nutsedge 30 80 90 30 . : ~ ` " ' : ; ' . ' ',' " ' ' ' 6~7 Table 8 (Cont.) Postemergence Herbicidal Activity Compound No.18 19 20 21 Rate (kg/ha)0.5 2.0 0.5 2.0 %K _%C %K %C %~ %C %K %C-SDecies . _ _ Cotton 100 100 90 80 Soybean 30 40 40 20 Field Corn 60 50 30 20 Rice 20 50 20 30 Wheat 20 30 30 20 Field Bindweed 50 80 40 90 Morningglory 50 90 80 100 VelvetleaE 80 100 100 100 ~arnyardgrass 10 80 80 40 Green Foxtail 60 80 60 30 Johnsongrass 30 40 10 40 Yellow Nutsedge 10 90 10 30 Compound No. 51 52 Rate (kg/ha) . 2.a _ 0 ~oK ~ ~%C 30K %C
Species _ ~
Cotton 70 100 Soybean 50 95 Field Corn 10 100 Rice 30 90 Wheat: 10 100 Field Bindweed 90 : 100 Morningglory100 : 100 Velvetleaf 90 100 arnyardgrass70 I00 Green Poxta:il 10 100 Johnsongrass40 100 Yel~low Nutsedge 0 ~ ~ 100 ~z~
Table 8 (Cont.) Postemer~ence Herbicidal Activity Compound No............. Al A2~ A3 Rate (kg/ha) 4.~0 2.0 2.0 ~K %C %~ %C %K %C
SDecies .___ _ _ Cotton 100 90 100 Soybean 0 20 0 Field Corn 0 30 0 Rice 30 20 90 Wheat 30 30 80 Field Bindweed 100 80 100 Morningglory 100 70 60 Velvetleaf 100 ND 100 Barnyardgrass 100 90 100 Green Foxtail 100 ND ND
Johnsongrass 75 60 95 Yellow Nutsedge 0 10 0 -.~: .
: Compound No. A4 A6 Bl B2 - Rate (kg/ha) 1.0 0.5 2.0 ~ r---%K %C %K %C %~ %C %K %C
Species _ ~
:
Cotton 100 90 100 100 : : Soybean 40 20 10 30 ~ Field Corn 40 20 40 30 .: : : Rice 20 30 50 80 ~heat 90 90 100 100 Field Bindweed90 10 100 100 : Morningglory100 90 100 40 : Velvetleaf 100 ~ 100 100 100 : Barnyardgrass100 100 100 100 Green Foxtail100 90 100 100 Johnsongrass 60 30 80 80 Yellow Nutsedge 100 : 50 40 80 ~: . .
~:: ~ : . - ., . : - , - 1 2g -Table 8 (Cont.) Postemergence Herbicidal Activity Compound No. B3 B4 B5 _ B6 Rate (kg/ha) ~ 2.0 1.0 2. 1.0~~~~~
%K ~C %X %C %K %C ~ %C
Species Cotton 100 100 100 100 Soybean 30 40 60 60 Field Corn 70 30 Z0 100 Rice 90 90 80 100 Wheat 90 100 90 100 Field Bindweed 100 100 100 90 Morningglory80 90 100 100 Velvetleaf 100 100 100 100 Barnyardgrass 100 100 100 100 Green Foxtail 100 100 100 100 Johnsongrass90 80 90 80 Yellow Nutsedge 30 90 60 100 ;
.
Compound-No. B7 B8 B10 Bll Rate (kg/ha)1.0 2.0 1.0 1.0 : %K %C %K ~ %C %K %C %~ %C
Species ~ ~
~ Cotton ~ 100 100 100 100 : : : Soybean 60 80 20 30 ~:~ Field Corn 100 70 0 0 ~: - Rice : 100 100 20 30 Wheat 100 100 10 100 : Field Bindweed 100 100 100 100 Morningglory 100 100 100 100 Yelvetleaf: 100 100 100 100 : Barnyardgrass 100 100 I00 : 100 Greèn Foxtail 100 100 100 100 Johnsongrass : : 80 :70 90 90 :Yellow Nutsedge 80 : 70 ~ 20 : 100 Table 8 (Cont.) Postemergence Herbicidal Activity Compound No.B12 B13_ B14 B15 Rate (kg/ha) 1;.0 l.0 1.0 2.0 ~ %K %C %K ~C
Species ~
Cotton 100 100 100 100 Soybean 30 .100 90 80 Field Corn 10 60 .20 60 Rice 20 50 80 90 Wheat 100 90 80 100 Field Bindweed100 100 90 100 Morningglory 100 lbO 90 lO0 Velvetleaf lO0 lO0 100 lO0 Barnyardgrass 100 lO0 100 100 Green Foxtail 100 lO0 100 lO0 Johnsongrass 30 lO0 60 lO0 Yellow Nutsedge90 100 70 90 .
:. .
, .
: Compound No.B16 B17 B18 ,B21 . Rate (kg/ha)1.0 1.0 2Ø 1.0 %~ %C %K %C %~ %C %K ~C
Species :: :
~ Cotton lO0 lO0 100 lO0 :~ Soybean 4a 40 50 30 Field Corn 30 30 20 30 : Rice 50 30 90 20 ~ Wheat 100 40 70 lO0 : : : Field BindweedlO0 lO0 lO0 lO0 Morningglory 80 90 lO0 lO0 Velvetleaf lO0 100 100 90 :Barnyardgrass100 70 lO0 lO0 Green FoxtaillO0 100 100 100 Johnsongrass 40 30 40 lO
: Yellow Nutsedge 100 : 60 90 80 ~: :
, ~
~, . , ~.: : .:... . .. ,.... ... . . -: . . . . . . .
~ :~ . ... . . . .
i$~
Table 8 (Cont.) Postemergence Herbiciclal Activity Compound No B22 B23 B25 B30 Ra-te (kg/haj~ - 1.0 1.0 b. 5 %~ %C ~K %~ %~ %C %K %C
Species _ ~
Cotton 30 100 80 80 Soybean 30 10 30 10 Field Corn 20 40 90 10 Rice 70 90 50 70 Wheat 90 80 90 100 Field Bindweed 50 100 lO0 50 Morningglory100 100 100 100 VelYetleaf 100 100 100 100 Barnyardgrass 100 60 100 100 Green Foxtail 100 100 100 100 Johnsongrass10 100 50 10 Yellow Nutsedge 10 90 90 10 .
Compound No.B31 B32 _B33 B50 Rate (kg/ha)1.0 O.S 1.0 o.5 %C ~ F %K %C %~ %C
Species Cotton 100 100 100 : 100 Soybean 20 10 30 30 Field Corn 40 0 40 20 Rice 40 20 40 40 Wheat 80 70 100 40 Field Bindweed 100 80 100 70 Morningglory90 100 100 100 Velvetleaf 90 100 100 100 Barnyardgrass 100 100 100 100 Green Foxtail 100 100 100 100 Johnsongrass50 0 40 :30 Yellow Nutse~dge 90: 0 :60 20 , :
, ~ , . ... ~ ... , - -~- ,, , ,, , :
.
. " . . :, - :: .. -: - : .;, ,- :: :
~6~i67 Table 8 (Cont.) Postemergence Herbicidal Activity Compound No. B57 Cl Rate (kgtha) 0.5 2.0 %K %~ %K ~C
SDecies .
Cotton 100 100 Soybean 30 30 ~ield Corn 30 70 Rice 90 20 Wheat 90 0 Field Bindweed80 100 Morningglory 100 100 Velvetleaf 100 100 Barnyardgrass 100 100 Green Foxtail 100 100 Johnsongrass 40 80 Yellow Nutsedge 60 60 : :
~: :
:~ .
` Compound No. . C2 C3: C4 C5 :: Rate (kg/ha) 1.0 2.0 , 2.0 2.0 %K %C %K %C %K %C
SDecies ;: . . - _ Cotton 100 100 70 100 Soybean 90 40 40 90 Field Corn 100 100 40 100 Rice : 100 70 50 100 Wheat100 40 30 100 Field Bindweed100 90 100 : 100 orningglory 100 100 90 100 Velvetleaf : 100 100100 100 Barnyardgrass 100 100 90 100 Green Foxtail 100 : 100 90 100 Johnsongrass 100 : 90 40 90 Yel~low Nutsedge 100 :30 20 100 , .,, ~, ~ ,., , ,, . , ~ . . , ~ ~ :: - . , . . .. . .. ..
- . . . . .
.~: ~ ~ : .. , . : , i7 Table 8 ~Cont.) Postemer~n_ _Herbi idal Activity Compound No. . C6 C7 C8 C9 Rate (kg/ha) 2.~ 1.0 2.0 1.0 %K %C %~ %C ~K %C %K %C
SDecies _ Cotton 100 100 100 90 Soybean 90 - 60 90 80 Field Corn 100 50 90 80 Rice 100 80 80 50 Wheat 100 10 80 60 Field-Bindweed 100 100 100 90 Morningglory 100 100 100 80 Velvetleaf 100 100 100 100 Barnyardgrass 100 100 60 100 Green Foxtail 100 100 100 100 Johnsongrass 100 90 80 90 Yellow Nutsedge 100 80 60 20 : ~
Compound No. C10 Cll Ci2 . C13 Rate (kg/ha) 1.0 1.0 1 2.0 %K~ %C %K %C %X %C %K %C
Species ~ ~
Cotton 100 100 100 100 Soybean 100 ~ 90 90 80 Field Corn 60 100 100 100 Rice 60 100 100 100 Wheat 60 100 100 100 Field Bindweed 60 ::90 100 ~ lQ0 Mo~ningglory : 100 100 100 100 Velvetleaf 100 : 100 100 100 Barnyardgrass 100 100 I00 100:
:Green:Foxtail 100 100 : 100 100 Johnsongrass: :80 90 100 100 Yellow:Nutsedge 10 100 100 ~ 100 i66~7 - 13~ -Table 8 (Cont ) Postemergence Herbicidal Activity Compound No. C14 Cl5 C16 C17 Rate (kg/ha) 2Ø Z.0 2.0 2.0 - %K %C %K ~C %K %C %~ %C
~ ~T _ ___ _______ r Cotton100100100 lO0 Soybean100 90 100 100 Field Corn100 90 100 100 Rice 70 5090 100 Wheat100 lO0100 100 Field Bindweed 100 100 100 90 Morningglory100 100 100 100 Velvetleaf100 100 100 100 Barnyardgrass 100 100 100 100 Green Foxtail 100 100 100 100 Johnsongrass100 90 100 50 Yellow Nutsedge 100 90 100 100 .
.~ .
Compound No. C18 Cl9 C20- C21 : ................. Rate (kg/ha) 1Ø1.0`- 1 0 1.0 : :................ %K - %C %K %C ~K~ C %X ~C
Svecies _ . _ : Cotton 100 100 100 100 Soybean 40 40 100 lO0 Field Corn 30 : Z0 0 100 :~ Rice 10 10 20 60 ;: Wheat 100 100 100 lO0 `` Field Bindweed 100 100 100 100 Morningglory 100 100 100 100 `~ Velyetleaf 100 100 lO0 100 ~ Barnyardgrass lO0 100 100 100 -~:- 5reen Foxtail 100 100 100 100 Johnsongrass 90 100 40 100 :Yellow Nutsed:ge 100 60 10 80 , ~
.:..
~ ~:
:~:: ~ :
:~;~: :
: : . ...
.
~2~
Table 8 (Cont.) Postemer~ence Herbicidal Activity Compound No. C22 C23 C24 C25 Rate (kg/ha) 1.0 ~ 1.0 2.0 %K %C %K %C %K %C %K %C
SD ecies ~ -_ _ , _ _ Cotton 100 100 50 100 Soybean lO0 80 20 70 Field CornlO0 80 20 60 Rice 80 30 lO 50 Wheat 100 90 10 60 Field Bindweed 100 100 100 100 Morningglory100 80 90 100 VelvetleaflO0 lO0 100 100 Barnyardgrass lO0 100 80 lO0 Green Foxtail lO0 lO0 lO0 100 Johnsongrass100 100 60 100 Yellow Nutsedge 80 40 0 70 .
:
~: , . . .
Compound No. C26 C32 C38 .
Rate (kg/ha)I.0 l.0 : ~ 1.0 ~: ~R~ g~ %K %C %K %C
sPecies ' ' ~ ~
:~ Cotton 100 lO0 lO0 ~: Soybean 80 80 lO0 Field CornlO0 20 lO0 Rice 90 50 lO0 ~ Wheat 90 50 100 :G : Field Rindweed l:00 lO0 70 Morningglory: 100lO0 lO0 Velvetleaf100 lO0 1:00 Barnyardgrass 100 100 100 : : Green Foxtail 100 80 100 : Johnsongrass90 40 90 Yellow:~utsedge 90 20 ND
.. , : : ~
Table 8 (Cont.) Postemergence Herbicidal Activity Compound No. C42 C43 C59 _ C69 Rate (kg/ha) ~---r~r-~ ---r~r~- ~K %C %K %C .
Species _ . .
Cotton 100 100 lO0 lO0 Soybean 100 90 80 50 Field Corn 100 100 80 80 Rice 60 50 40 60 Wheat 90 95 80 90 Field Bindweed 100 100 100 100 Morningglory 95 .100 100 100 Velvetleaf 100 100 100 100 Barnyardgrass 95 100 100 100 Green Foxtail 100 100 100 50 Johnsongrass 95 100 95 60 Yellow Nutsedge40 95 100 50 : .
. . . .
: Compound No. C70 C71 . C72 C73 : Rate (kg/ha) 1.~ 1.0 1.0 1.0 %K ~ %C 30~ ~ %C %K %C
Species : : : Cotton 90 100 100 100 Soybean 60 60 70 : :85 :.~ Field Corn 40 60 50 30 :Rice 30 40 60 60 : : :Wheat 40 95 30 80 : Field Bindweed 100 :100 100 100 Morningglory lO0 100 : 100 : 100 Velvetlea~ 100 : 100 : 100 100 : : Barnyardgrass1:00:~ 100 100 90 ~ Green~Foxta:il 30 100 : 60 ~ 90 7~ : Johnsongrass 70 50 50 70 ~ Yéllow Nutsedge 40 : 20 ~ :60 30 ~6~;~7 Table 8 (Cont.) Postemergence Herbicidal Activit~
Compound No. C74 C75 C76 C77 Rate (kg/ha) 1.0 1.0 1.0 1.0 %K O~C ~ %K %C %K %C
: S Dec i e s ~ . . _ ~
Cotton 85 95 95 100 Soybean 90 90 80 80 Field Corn 40 100 70 100 Rice 60 40 40 30 Wheat S0 40 30 100 Field Bindweed 95 100 -100 100 Morningglory100 100 95 100 Velvetleaf100 100 100 100 Barnyardgrass 100 95 95 95 Green Foxtail 85 100 95 100 Johnsongrass50 80 40 70 Yellow Nutsedge 30 10 20 30 . .
Co~pound No. C78 C79 C80 C81 Rate (kg/ha) ~ 1.0~~~.0 1.0: 1.0 %~ %C %K %C %K ~C %K %C
Species . .
Cotton 100 100 100 100 Soybean 100 50 80 100 Field Corn 100: 20 40 80 Rice 30 20 10 90 Wheat 90 40 40 95 Field Bindweed 100 50 100 100 Morningglory 100 60 100 100 VelYetleaf 100 100 100 100 Barnyardgrass 100 100 40 100 Green Foxtail 90 95 100 100 Johnsongrass 60 80 40 100 Yellow Nutsedge 20 70 20 20 : : :
~ :
,.: ~ :
. r ,: ' ' ` ' . ` `' ,.,. "'''. . ' ','' ' . " .`'' `
' ~ : "' : '' ", ' ' '' . ~,,:' ;~2~i6;6~
Table 8 (Cont.) Postemergence Herbicidal Activity Compound No.C82 C83 C84 C85 Rate (kg/ha)~~~~~~ ~ 1.0 1.0 1.0 ~o ~ % C % ~ % C % ~ % C ~ol~ % C
SDecies Cotton 100 100 80 100 Soybean 80 100 40 90 Field Corn 100 95 40 95 Rice 70 60 20 95 Wheat 90 90 30 80 Field Bindweed 100 .100 20 95 Morningglory100 100 90 100 Velvetleaf 100 100 100 100 Barnyardgrass 100 10095 100 Green Foxtail 100 10030 100 Johnsongrass 100 95 20 90 Yellow Nutsedge 0 60 ND ND
, .
. . .
Compound No. C86 C87 C88. C89 Rate (kg/ha) 2.0 ~ 1.0 1.0 ------~~K %C %K: %C
Species Cotton 100 90 10 90 Soybean 80 100 30 90 Field Corn 100 100 20 100 Rice 100 50 10 70 Wheat : 100 60 I0 100 Field Bindweed~ 100 100 10 95 Morningglory 100 100 20 100 Velvetleaf - 100 100 20 lO0 Barnyardgrass : 100 100 20 100 Green Foxtail 100 80 50 100 Johnsongras:s 100 30 30 80 Yellow:Nutsedge ND~ ND ND ND
.. . .. . . . ~ . . . . . ... .. . . .
66~7 Table 8 (Cont.) Postemergence Herbicidal Activity Compound No. C90 C91 C92 _C93 Rate (kg/ha) 1.0 1.0 1.0 1.0 %K %C %K %C %~ %C %~ %C
Species ~_ _ Cotton 100 100 100 100 Soybean 100 100 90 70 Field Corn 95 100 100 70 Rice 60 90 70 30 Wheat 100 100 80 80 Field Bindweed 100 100 100 70 Morningglory 100 100 100 95 Velvetleaf 100 lO0 100 100 Barnyardgrass 100 lO0 100 100 Green Foxtail 100 100 80 95 Johnsongrass 100 100 70 30 Yellow Nutsedge ND ND ND ND
Compound No. C94 C95. C97- C98 Rate (kg/ha) 1.0 1.0 l.0 0.5 %K %C %K %C %K %C %K %C
S~ecies Cotton 100 100 95 90 Soybean 80 95 95 70 Field Corn 50 95 lO0 70 Rice ~ 30 70 95 70 Wheat 40 100 100 90 Field Bindweed 95 100 95 100 Morningglbry 100 lO0 100 l00 Velvetleaf lO0 100 100 100 Barnyardgrass 80 90 95 95 Green Fox~tail 95 100 lO0 70 Johnsongrass 60 70 95 90 Yellow Nutsedge ND ND ND ~ ND
: . ~
.....
~: ,. , ~, - : , -: , : -Table 8 (Cont.) Postemergen_ _Herbicidal Activit~
Compound No. C99 C100 C101 C102 Rate (kg/ha) 0.5 0.5 0.5 0.5 %K ~C %K %C %K %C %K %C
Specles Cotton 90 100 100 100 Soybean 100 100 60 50 Field Corn 100 100 50 60 Rice 40 40 20 70 Wheat 100 100 40 95 Field Bindweed 100 100 90 90 Morningglory 100 100 90 100 Velvetleaf 100 100 100 95 Barnyardgrass 100 100 30 60 Green Foxtail 90 100 10 100 Johnsongrass 100 90 50 70 Yellow Nutsedge ND ND ND ND
. ' . . .
Compound No. ~ C103. C104 C105 C1.06 Rate (kg/ha) 0.5 0.~ 0.5 0.5 ~o~ R~ %~ %C %K %C
S~ecies ~
Cotton 100 80 100 100 Soybean 30 80 100 100 Field Corn 30 90 95 100 Rice 40 70 95 95 Wheat 30 90 1:00 100 Fi:eld:Bindweed 95 50 100 : 100 Morningglory 95 90 100 100 Velvet:leaf 100 100 100 100 Barnyardgrass 60 95 100 100 Green Foxtail 100 9S 100 100 Johns:ongrass 70 80 100 100 Yellow Nutsedge ND ~ ND ND ND
~. :. ., : , . .
6q:~7 Table 8 (Cont.) Postemergence Herbicidal Activity Compound No. Cl07 C108 C109 CllO
Rate (kg/ha) 0.5 0.5 0 5 0.5 -~Rr~ K %C %K %C %K %C_ Species Cotton 100 100 95 80 Soybean 60 100 95 100 Field Corn 60 100 80 90 Rice 20 95 80 80 Wheat 20 100 95 95 Field Bindweed 100 100 100 100 Morningglory 100 100 100 100 Velvetleaf 100 100 lO0 100 Barnyardgrass95 100 100 100 Green Foxtail90 100 100 100 Johnsongrass 60 100 100 100 Yellow Nutsedge ND ND ND ND
.. ..
.
... . . .
Compound No.Clll Cl12 C113 C114 .
:: Rate (kg/ha) 0.5 0.5 0.5 `0.5~~
. %K _ %C ~K %C ~K %C %~ %C
:~-, S DeC i e s :::, Cotton 40 90 80 95 Soybean 50 90 40 50 ~ Field Corn 20 : 40 30 30 :~: : Rice 20 20 30 80 ~: Wheat 70 90 30 30 Field Bindweed 60 : 100 100 lO0 ,m - ~ Morningglory 100 lO0 lO0 100 :~ Velvetleaf100 ~ 100 100 lO0 Barnyardgrass 100 9:5 30 70 :: ~ Green Foxtail 100 ~ lO0 80 90 : Johnsongrass ~::95 95 40 30 Yellow Nutsedge ND ND ND ND
~:: : - ,, . : : , ,~ , . :
Table 8 (Cont.) Poste er~ence Herbicidal Ac_ivity Compound No. C115 C116 C117 C118 Rate (kg/ha) 0.5 0~ O.S 0.5 ~ K %C %K %C %K %C %~ %C
Species . . _ _ _ _ _ Cotton 20 100 100 40 Soybean 30 60 100 95 Field Corn 30 40 100 100 Rice 10 20 0 10 Wheat 30 60 95 60 Field Bindweed 10 80 100 95 Morningglory 30 100 100 80 Velvetleaf 20 100 lO0 100 Barnyardgrass 20 70 100 60 Green Foxtail 30 70 100 40 Johnsongrass - 30 80 70 20 Yellow Nutsedge ND ND ND . ND
Compound No. Cll~ C120 C121 C122~ . :
Rate (kg/ha) 0.5 ~ S~- 0.5 0.5 %K ~C %K ~C %K %C
Species _ _ -Cotton 95 80 100 95 Soybean 95 95 80 80 Field Corn 40 60 10 60 Rice 10 10 20 10 ~heat : 90 100 100 100 Fie}d Bindweed 100 100 100 95:
Morningglory: 100 : 100 , 100 100 Velvetleaf 100 100 100 100 Barnya:rdgrass 50 50 80 100 Green Foxtail 70: 20 30 80 Johnsongrass ~ 60 40 : 80 80 Yellow Nutsedge ND ND ND: ND
:~......... . :- ,, ,; ~ :
~;: : : , ~ , ; . , :: ~ ,..-: :
;6~7 Table 8 (Cont.) Postemergenc _Herbicidal Activ_ty Compound No. C123 C124_ C125 Rate (kg/ha) 0.25 0.5 -~~ 5 % K % C % X% C % K% C
Species Cotton 100 100 100 Soybean 100 100 100 Field Corn 90 100 100 Rice 90 70 Wheat 100 100 100 Field Bindweed 100 100 100 Morningglory 100 100 100 - Velvetleaf 100 100 100 Barnyardgrass 95 100 95 Green Foxtail 95 100 95 Johnsongrass 95 95 90 Yellow Nutsedge ND ND ND
: . :
; .
:
: ~: : . :
:
~ 08~33W30080Wmd~
58Hz), 7.48 (s,lH), 7.50 (s,lH).
A2 50-55 Cl3HllclF3N3o4 NMR ~ (CD C13j: 1.70 (m,3H), 4.80 (m,1H), 2.40 (s,3H), 7.10-7.50 (m,3H), 8.00 (bs,lH) A3 S6-60 C14H14ClF2N304 N M R ô ( C D C13): 1.60 (d,3H,J=7Hz), 2.30 (s,3H), 2.50 (s,3H~, 4.70 (q,lH~J=7Hz), 6.80 (2,1H), 7.00 (t,1H,J=58Hz), 7.30 ts,1H), 8.30 (s,1H).
A4 Solid ~ ~ C 13HloClF3N 3NaO 4 A5 130-132C12HgClF3N304 H20 C 38.99 3.00 11.37 F 38.95 2.91 11.23 A6 ~ 70-75 C 16H 20 c lF 3N 4o 4 ~6~i~67 TAB L E 6 ( C ontinued) C mpd. Melting Ele m ental Analysis No. Point (C) E mpincal Form~a C H N
Bl Oil C16H16C12F2N406 - N M R~ ( C D C13): 1.40-1.80 (m ,6H), 2.50 (s,3H), 4.40-5.00 (m,4H), 7.00 (s,lH), 7.10 (t,lH,J~
581iz), 7.60 (s,lH).
B2 Oil C16H15Cl2F2N304 C 45.52 3.58 9.95 F 45.24 3.46 9.87 NMRô (CDC13): 1.70 (d,3H,J=7Hz), 2.50 (s,3H), 4.60-5.00 (m,3H), 5.10-5.40 (m,2H), 5.50-6.20 (m,lH), 7.00 (s,lH), 7.10 (t,lH,J=58Hz), 7.60 (s,lH).
B3 Oil C16Hl3cl2F2N304 NMR~(CDC13): 1.70(d,3H,J-7Hz), 2.50(bs,4H), 4.60-A90 (m,3H), 6.95 (s,lH), 7.05 (t,lH,J ~58Hz), 7.60 (s,lH).
B4 Oil C}6H13ClF3N304 C 47.60 3.24 10.41 F 47.88 3.31 9.68 NMR~ (CDC13): 1.65 (d,3H,J=7Hz), 2.45 (m,4H), 4.70(m,3H), 7.05~(t,1H,J-58Hz), 7.10-7.40 (m,2H) B 5 Solid C 16H17Cl2F 2N 30 5 B6 Oil C17H15ClF3N304 C 48.87 3.62 10.06 F 46.60 3.19 10.01 B7 0 C18Hl7ClF3N3o4 C 50.07 3.97 9.73 F 49.68 3.75 9.40 ~ : `
B8 OiI ~ ClgHlgclF3N305 C 48.06 4.26 9.34 F 48.31 3.77 9.00 B 9 Oil ~ C 16 HI s ClF 3N 30 BIO~ Oil ~ C 18Hl 7clF7N 30 4 s~ ail ClSH12ClF3N404 Bl2 ~ 0il ~ ClgHlsclF3N30s B 13 ~ ~ Oil ~ ~ ~ C 17 H 20 ClF 3N 40 4 .. .. . .. ..
6~
TABLE 6 (Continued) C m pd. M elting Ele m ental Analysis No. Point (C) Empirical Formula C H N
.
Bl 4 Oil C 1 7H1 7 ClF 3N 3O 5 B15 Oil ClgHl5clF3N3O4 C51.66 3.42 9.51 F52.15 3.43 9.49 BI6 Solid Cl7Hl5clF3N3O6 C45.40 3.36 9.34 F45.00 3.25 8.90 B17 Oil Cl5HlsclF3M3o3s B18 O;l C17Hl7clF3N3O5s C43.64 3.66 8.98 F43.50 3.73 7.99 Bl9 Oil C14H12C12F3N3O4 NMR~ tCDC13): 1.40 (t,3H,J=7Hz), 2.50 (s,3H), 4.45 (q,2H,J=7Hz), 5.95 (d,lH,J=58Hz), 7.40 (s,lH), 7.50 (t,lH,J=58Hz), 7.65 (s,lH).
B21 131-136 ClgH22clF3N4os B22 Oil ClsH15ClF3N3O5 B23 Oil ClsH15ClF3N3O4S
B25 Solid ClsHlsclF3N3o6s C39.36 3.30 9.18 F39.25 3.00 9.22 B30 Oil ClsHl2clF6N3O4 B31 Oil C17Hl6clF3N4O4 :
B32 Oil C20Hl7clF3N3o4 B33 Oil ~ C16H17ClF3N3O3S
B50 Oil ~ C20Hl7clF3N3o4s B57 Oil Cl7Hl7clF3N3o6 C45.19 3.79 9.30 F45.68 3.77 8.22 Cl 209-210 ~ C12HloCl2F2N4O3 NMR~ CD C13/D MSO ~ d6): 2.20 (s,3H), 4.60 (s,2H), 7.30 (bs,3H), 7.40 (5,1H,J=58Hz), 7.65 (s,1H).
, ~ :
3LZ66~ 7 .
TABLE 6 (Continued) C m pd. M elting Ele m ental Analysis No. Point (C) Em~ilic Form-da C H N
C 2 Oil.C 14Hl 4 ClF 3N 40 3 N M R ~ ( C D C13): 1.60 (d,3H,J-7Hz), 2.50 (s,3H), 2.90 (d,3H,J=7Hz), 4.75 (q,lH,J=7Hz), 6.80 (bs,lH), 7.10 (t,lH,J=58Hz), 7.20-7.45 (m,2H).
C3 185-188C14H14C12F2N4O5S C 36.61 3.07 12.20 F 36.79 3.01 12.41 NMR~ (CDC13): 1.70 (d,3H,J=7Hz), 2.50 (s,3H), 3.40 (s,3H), A80 (q,lH,J=7Hz), 7.10 (s,lH), 7.10 (t,lH,J=58Hz), 7.70 (s,lH).
C4 OilC14HllC12F5N4O5S C 32.76 2.16 lQ92 F 32.80 2.05 8.77 NMR~ (CDC13): 1.70 ~d,3H,J=7Hz), 2.50 (s,3H), 7 60 ~1HHjJ875Hoz~ 7ilHO)(s,lH), 7.10 k,lH,J=58Hz), . , , . :.
C5 132-135 C13Hl2cl2F2N4O3 C 6 142 -144 C 14 H14 Ci2 F 2 N 40 3 C7 173-175 C12HloclF3N4o3 C8 105-110 C16Hl8clF3N4O3 C9 Oil C17H20ClF3N403 C10 Solid;~ C2oHl8clF3N4o5s C 46.29 3.50 10.80 F 46.77 4.12 ~ 11.03 ClI Oi1 ClsHl6clF3N4O4 C 44.07 3.94 13.71 F 38.44 3.67 11.28 C12 Solid~ C16Hl4clF3N4O3 ~ C 47.71 3.50 13.91 F 46.03 3.60 13.91 C13 57 ~ C19~16CIF3N~43 C 51.77 3.66 12.71 F ~50.90 4.00 11.88 C1~4~ ~Oil ~ ClsH16CIF3N43 ;
C15 ~Solid ; C17H20ClF3N 40 C16~ Oil ClsHl6clF3N403 6~;~
TABLE6 (Con~nued) Cmpd. Melting E~emental Analysis No. Point(C) Empincal Form~a C H N
C17 So~d Cl6Hl6clF3N4os C18 145-150 C14Hl4clF3N4O5s Cl9 Solid C14H14C1~3N4NaO5S
C20 So~d C2oHl7clF3N4Nao5s C21 Oil C18Hl8clF3N4O3 C 50.18 4.21 13.00 F 50.95 3.91 12.38 C22 Oil Cl7Hl7clF3Nso3 C23 O~ C20Hl8clF3N4o3 C25 So~d Cl9H15C12F3N45S C 42.31 2.80 10.39 F 40.44 2.91 8.S6 C2~ 142-143 C13Hl2clF3N4O3 C32 127-134 ClgH16ClF3N4O5S
C38 47-54 C17Hl8clF3N4O3 C 48.75 4.33 13.38 F 47.06 3.73 12.36 C42 O~ C21HlgclF3N4O5s C43 162-166 Cl9H15C12F3N45S
C59 100-105 C2lHlgclF3N4o7s C 44.81 3.40 9.95 F 42.20 2.81 9~61 :
C69 SoW ClgHl6clF3N4O5s C 45.20 3.19 11.10 F 44.74 3.55 10.59 C70~ 208-208.5 ~ C18H13Cl2F3N45S C 41.16 2.49 10.67 F 44.11 3.08 10.96 C71 ~ So~d~ ~ Clg~14C12F3N4 5SNa C72 ~135-i40 C20H18ClF3N4O5S
C73~So~d ClgH15Cl2F3N4O5s C74 110 ClgH15ClF3N507S
'' : `, : I . :
Q.~ 7 TABLE 6 (Continued) Cmpd. ~lelting Elemental Analy~s No. Point ~C) Empirical Formula C H N
C75 175-180 ClgH14C13F3N405s C76 171-173 Cl9H15C13F2N45S
C77 66-70 ClgHlsClF4N405S
C78 248-Z53 C22H22ClF3N4o5s C79 Solid C21H20ClF3N4O5S
C80 67-70 C20HlsClF6N40 5S
C81 58-62 C20Hl8clF3N4o6s C82 Solid C20HlgClF3N4O5S
C83 108-113 C20H17ClF3N46SNa C84 155-157 C20H17C12F3N45S C43.413.1010.13 F42.653.309.I9 ~ . ., C85 69-74 C17Hl4clF3N4O5s2 ,::
~-; C86 Solid ClgH20clF3N4o5 ,.
C87 Solid C23H24ClF3N405s C49.244.319.99 F46.404.218.63 C88 Solid ~ ClgHl7C12FN405S
C89 So~id C18H18ClF3N 4O5 C90 168-172 C21H20ClF3N407S
C91 Solid C21HlgClF3N~407SNa C9Z~ Sohd ~ C20H17ClF3N40sSNa C93 ~173-179 C21HlgclF3N407s C94 65-70~ Cl9H15C12F3N45S
C95 110 ~ ClgHlsBrC1~3N4OsS C 39.092.59 9.60 F38.752.669.64 C97 ~ Solid ~ C2oH22clF3N4os TABL E 6 ( Continued) Cmpd. Melting Element~l Analy~is No. Point (C) Empirical Formula C H N
C98 Solid C 21H17ClF3N qO 7SNa C 99 Solid C 20H1 7BrClF 3N 40 6S
C100 Solid C2oHl6BrclF3N4o6sNa C101 Solid C20HlsClF3N505s C45.33 2.85 13.22 F44.83 2.42 13.06 C102 60-70 C18Hl8clF3N405s C43~69 3.67 11.32 F43.2q 4.01 10.71 Cl03 80-95 Cl~Hl8clF3N407s Cl04 Oil C21H2qclF3N4O5 C 105 Solid C 21 H 20 ClF 3N 4O 7S
Cl06 Solid C21HlgClF3N407SNa C107 170 Cl9HlsClF3l~l5075 C108 Solid C l gHl gClF 3N 50 4 ClO9 01l C22H22ClF3N406S
Cll0 85-90 C2zH21ClF3N406SNa Clll Oil ClgHl6clF3N406s C112 174-176 C20H18ClF3N407S
C113 Oil ~ ~ C20H17C12P3N405S
C114 60-70 ~ C20H16C12F3N405SNa ~:."
C115 ~Solid~ ClgHl sBrClF3N 40 sS
C116 ~ 188-191 C20H16ClF3N47 Cl17 ~ >230 C23HlgClF3NqOss c11~8 ~ 144-147~ C21HIgCl3F2N4o7s Cll9 ~ 211-212 ~ C20H18CIF3N407S
~ ~ , ~ . , . . . :. , , "
- 105 ~
TABLE 6 (Continued) C m pd. M elting Ele m ental Analysis No. Point (~C) Empincal Form~a C H N
C120 Solid C2oHl7clF3N4o7sNa C121 Solid C20Hl7ClF3N4O7SNa C122 105-110 C2lH2ocl2F2N4o7s C123 163-166 C21H2OBrF3N4SO7 C124 Solid CzlH21ClF3N5O5S
C125 Solid C20Hl5clF6N4o6s C126 Solid C 20H17ClF3N 5O 7s C127 Solid C2gH34ClF3N4F3O5s C128 Solid C2gH33ClF3N4OsSNa : .
C129 147-149 C19H16C1F3N4O6S C 43.81 3.10 10.76 : . : . F44.31 3.26 10.54 ,~ . . . . .
C130 Solid ClgHlsClF3N 4O 6SNa C131 198-20I C23H22C1F3N4O6S C 48.05 3.86 9.74 F 47.11 3.89 9.34 C132 Solid C20H14C1F6N4O6SNa C133 Solid C2OH15BrF6N4O6S
C136 Solid C21H20C1F3N406S
CI38 136-140 ~ C23HIaCIF3N4O55 C139 Solid ~ C21H19CIF3N4O6SNa 0833W30080W md ~ ~
i6~
- 10~ -Table_7 P_eemergence Herbicidal Activity Compound No.1 2 3 4 - Rate (kg/ha) 2.0 4.b ~ r---%K %C %K %C %K ~ %K %C
Species , Cotton 100 100 10050 Soybean 0 90 30 0 Field Corn 80 100 10030 Rice 50 100 90 30 Wheat 0 100 10030 Field Bindweed100 100 100100 Morningglory 100 100 60 0 Velvetleaf 100 100 ND100 Barnyardgrass 90 100 100100 Green Foxtail100 100 100ND
Johnsongrass 80 100 10095 Yellow Nutsedge70 100 100 0 ~, ' , .
Compound No. _ 6 7 _ 8 9 Rate (kg/ha) 2.:0 2.02.0 ~ 2.0 ~
~R~ %K %C %K %C %~ %c Species _ --Cotton 100 60 70 100 Soybean 10 30 20 20 Field Corn 70 30 20 80 Rice 80 50 60 90 Wheat 100 80 40 90 Field:Bindweed 100 60 80 100 Morningglory 100 ~ 70 90 100 Velvetleaf :: 100 100 100 100 Barnyardgrass 100 100 100 100 Green Foxtail 100 100 100 100 Johnsongrass ~ 90 90 90 100 Yellow Nutsedge 10-0 ~50 80 100 Table 7 (Cont.) Preemer~e~ rrbicidal Activity Compound No.10 11 12 13 Rate (kg/ha)2.0 2.0 2.0 2.0 ~K~ %C ~R~ R~ 'n~---SDecies ~ ~
Cotton 100 40 100 30 Soybean 20 lO0 30 20 - Field Corn100 40 20 20 Rice 90 90 70 10 Wheat 90 70 50 .10 Pield Bindweed 100 100 90 20 Morningglory100 100 100 50 Velvetleaf100 100 100 80 Barnyardgrass 100 100 lO0 40 Green Foxtail 100 100 100 40 Johnsongrass100 100 90 40 Yellow Nutsedge 100 90 90 lO
. ' .
.
Compound No. 14 15 16 17 ~ :: Rate (kg/ha) 1.0 1.0 1.0 ~ r---:~- %~ %C ~R~ %K %C %K %C
~ Species ;
~:: Cotton 90 100 lO0 100 ~-~ Soybean 0 40 30 0 ~:: Field Corn 60 40 100 30 :~ Rice 30 80 90 30 - : : : Wheat 20 100lO0lO
` Field Bindweed lO0 90 100 90 : Morningglory 90 100 90 90 Velvetleaf 100 100 100 90 Barnyardgrass::50 : 100 100 90 Green Foxtail 10 100 lO0 lO
Johnsongrass 60 : : 90 90 80 :; Yellow Nutsedge ~ 100 90 lO0 60 ::;: ~ , Table 7 (Cont.~
Preemer~ence Herbicidal Activity Compound No. 18 19 20 21 Rate (kg/ha) 0.5 2.0 0.5 2.0 ~ %K %C %K %C ~ n~--Species Cotton ` 10 80 30 80 Soybean 20 100 0 20 Field Corn lO 80 0 80 Rice 0 90 20 30 Wheat 0 50 0 o Field Bindweed 0 lO0 . 90 lO0 Morningglory 0 90 90 90 Velvetleaf 30 lO0 lO0 lO0 Barnyardgrass 0 100 50 100 Green Foxtail 90 lO0 lO0 100 Johnsongrass 0 90 30 90 Yellow Nutsedge 0 lO0 lO 70 . . :
Compound No. 51 . 52 .
Rate (kg/ha) 2.0 2.0 : %K ~C %K %C
Species: _ _ :
Cotton : 70 : 100 Soybean lO : 70 Field Corn . 30 100 Rice ~ 40 ~ 95 Wheat 0 : 100 ~ :
Field Bindweed 90 lO0 Morningglory 80 ~ 95 ;Velvetlea~ : :lO0: 100 ~ :
Barnyardgrass 30: 100 Green ~oxt:ail : 20 lO0 Johnsongrass : 80 100 Yellow Nutsedge: 40 100 6~7 Table 7 (Cont.) Preemergence Herbicidal Activity Compound No. Al' A2 A3 Rate (kg/ha) 4.0 2.0 2.0 ~ %K ~%C %K %C
Species Cotton 100 10 80 Soybean 0 0 20 Field Corn 0 0 Rice 80 10 70 Wheat 80 20 100 Field Bindweed 100 30 50 Morningglory . 100 10 0 Velvetleaf 100 ND 100 Barnyardgrass 100 40 100 Green Foxtail 100 100 ND
Johnsongrass 80 30 95 Yellow Nutsedge 90 20 0 :
~: Compound No. A4 ~A6 Bl B2 Rate:(kg/ha) . 1.0 0 5 2.0 2.0 ~ %K %C %K %C %K %C_ : ~:: ` Spec es :.~
~- Cotton 90 80 100 100 ~: Soybean 10 30 10 10 : Field Corn 40 30 30 90 ~ Rice 80 30 90 90 : Wheat 80: 30 70 90 : : ~ Field ~indweed 70 70 I00 100 Morningglory~ 90 90 100 100 Velvetleaf 100 90 100 100 : ~ Barnyardgrass 100 100 100 100 Green Foxtail 100 : 100 100 100 :Johnsongrass 90 : 80 90 100 : Yellow Nutsedge 90 80 100 100 ; ~ , . , . . , . ~ . .. ..
: ,~: . : . . .. .
~6~7 Table 7 (Cont.) Preemergence Herbicidal Activity Compound No. B3 B4 _ B5 B6 Rate (kg/ha) 2.0- . 1.0 2.0 1.0 %K %C %R %C %K %C %~ %C
Species Cotton 100 90 100 100 Soybean 0 40 20 10 Field Corn 30 80 50 40 Rice 70 80 90 90 Wheat 80 90 90 90 Field Bindweed 90 100 100 90 Morningglory 100 90 90 100 Velvetleaf 100 100 100 100 Barnyardgrass 100 100 100 100 Green Foxtail 100 100 100 100 Johnsongrass 100 90 100 90 Yellow Nutsedge 100 90 100 100 Compound No. B7 B8 B9 B10 Rate (kg/ha) 1.02.0 0.5 1.0 ~
%K ~C ~ ~C %K ~C %K %C
Species Cotton 100 100 100 20 Soybean 30 50 20 0 Field Corn 80 100 30 30 Rice 90 90 60 30 Wheat 80 90 40 70 Field Bindweed: lQ0 100 80 100 Morningglory 100 100 60 90 :Velvetleaf 100 : 100 100 100 Barnrardgrass 100 ~~ 100 100 100 Green Foxtail ~ .100 100 :100 100 Johnsongrass~: : : 80:: 100 50 :80 Yel;low Nutsedge100;100 ~ : 10~0 70 6~:i7 Table 7 ~Cont ) Preemergence Herbicidal Activity Compound No.Bll B12 B13 B14 Rate (kg/ha)1.0 l.0 1 0 1 0 Species ~r~ T~ %~ ~C ~----R~ ~K ' ~C
Cotton 100 lO0 90 100 Soybean 10 10 100 20 Field Corn 60 20 90 40 Rice 60 60 90 80 Wheat 90 50 90 go Field Bindweed 100 70 100 90 Morningglory 90 90 100 lO0 Velvetleaf lO0 lO0 100 100 Barnyardgrass 100 100 100 100 Green Foxtail 100 100 100 100 Johnsongrass 90 80 90 90 Yellow Nutsedge 100 90 90 90 , Compound No. B15 B16 : B17 B18 Rate (kg/ha): ~2.0 I.0 -- I.0 -- 2.-0 S e~ies ~~ %C %K %C: %K %C ~%~ %C
~ : : P -- -- . .
Cotton 100 80 ::100 100 Soybean 70 : 20 40 : 30 Field Corn 90 60 80 60 Rice ~ 90 :60 80 80 Wheat 90 50 90 90 Field Bindweed 100 :90 80 100 Morningglory 100 100 100 100 VelvetIeaf :: 100::: :: 100 100 : 100 Barnyardgrass 100 : 100 100 100 :Green::Foxtail :10:0:: 100 : 90: 100 Johnson`grass:~ 100 ~90 :90 90 Yel~low:Nutsedge 100 ~ 100 :100 100 ~: ~ . ~ .. . .
. . ~ .
Table 7 (Cont.) Preemergence Herbicidal Activity Compound No. B21 B22 B23 B25 Rate (kg/ha) 1.0 0.5 1.0 _1.0 %K %C %K _ %C %X %C %X %C
SDecies Cotton 90 60 70 70 Soybean 0 0 0 50 Field Corn 50 0 30 70 Rice 40 40 80 60 Wheat 50 10 60 50 Field Bindweed 90 20 90 70 Morningglory 90 40 100 100 Velvetleaf 100 100 100 100 Barnyardgrass 100 ~0 90 100 Green Foxtail 90 80 100 100 Johnsongrass 40 20 70 90 Yellow Nutsedge 90 90 80 90 .
: . Compound No. B30 _ B31_ B32 B3~3 Rate (kg/ha) 0.5 1.00. 5 1~ 0 %K ~ %C %K%C %K%C %X%C
SDecies : Cotton 100 100 20 : 80 ~ Soybean 0 10 : 0 40 :~:: Field Corn 10 :20 20 90 Rice : 20: 50 20 90 Wheat 20 30 10 60 Field Bindweed 20 70 30 90 Morningglory :50 80 30 90 - Velvetlea~ 100 100 90: 100 Barnyardgrass 100 100 100 100 : : : Green Foxtail:: : 100: 100 100 100 Johns o ng ra s s ~: ~ 5 0 8 0 S 0 : 7 0 :~2:~ : Yellow Nutsed~ge ~100 :~90 ~ 90 90 ~;~66~
Table 7 (Cont.) Preemergence ~erbicidal Activity Compound No. B50 B57 Rate (kg/ha) 0.5 0.5 %C %K %C
Species Cotton 50 100 Soybean 20 10 Field Corn 30 40 Rice 40 50 Wheat 60 60 Field Bindweed 10 90 Morningglory 50 70 Velvetleaf 100 100 Barnyardgrass 90 100 Green Foxtail 100 100 Johnsongrass 50 70 Yellow Nutsedge 50 90 . .
:~
: . ,Compo~nd No _Ci C2 C3 C4 Rate (kg/haj 2~ 1.0%C ~ F %K2-0%C
; Species ~: Cotton 70 lO0 100 40 ;~ Soybean 40 100 40 0 Field Corn 60 100 80 0 : : Rice : 20 100 80 0 :~ Wheat 20 100 90 40 Field Bindweed 100 100 100 80 ~ : ~Morningglory . 100 100 100 90 :~ Velvetleaf 100 lO0 100 lO0 : Barnyardgrass 80 100 100 90 : Green Foxtail 90 lO0 100 90 . Johnsongrass 80 ~ 100 100 50 :: Yellow~Nutsedge 80 100 100 50 : :~
: : :
. ~ ~
:, ~ , : ' Table 7 (Cont.) Preemergence Herbicidal Activity Compound No. C5 C6 C7 _ C8 Rate (kg/ha) 2.0 2 0~ 1.0- 2.0 %K ~OC %~ ~C %K %C %K %C
Species ____ ___ _ _ _ _ _ Cotton 100 100 100 90 Soybean 100 90 10 100 Field Corn 100 100 100 100 Rice 100 100 40 100 Wheat 100 I00 30 100 Field Bindweed 100 100 100 100 Morningglory 100 90 100 100 Velvetleaf 100 100 100 100 Barnyardgrass 100 100 100 100 Green Foxtail 100 100 90 100 Johnsongrass 100 100 90 100 Yellow Nutsedge 100 100 100 90 .
: . - .
.. Compound No. C9 C10 Cll C12 Rate (kg/ha) 1.0 ~~~ ~~ :1.0 1.0 ~:~ %K %~ %K %C %K %C %K %C
i Species ::~ Cotton 80 100 100 100 : Soybean 90: 90 100 100 ~ Field Corn 100 20 100 100 .- Rice 90 80 100 100 ` : Wheat 100 70 100 100 : : FieId Bindweed 100 ~ 100 100 100 : Morningglory100 100 100 100 : Yelretleaf 100 100 100 100 : Barnyardgrass100 lQ0 100 100 ~:: : Green Foxtail100 :100 ~ 100 100 Johnsongrass100 90 100 100 Yellow Nutsedge 80 ~ 60 100 100 - llS -Table 7 (Cont.) Preemergence Herbicidal Activity Compound No._C13 C14 C15 C16 Rate (kg/ha)2.0 2.0 2.0 2.0 %~ %C %~------%C %R %C %K %C
Species Cotton 100 100 100 100 Soybean 100 100- 100 100 Field Corn 90 100 100 100 Rice 100 100 100 100 Wheat .90 100 100 100 ~ield Bindweed 100 100 100 100 Morningglory 100 100 100 100 :: Velvetleaf 100 100 100 100 Barnyardgrass 100 100 100 100 Green Foxtail 100 100 100 100 Johnsongrass 100 100 100 100 :~ Yellow Nutsedge 100 100 100 100 ~, .
.' :
~ . Compound ~o. C17 C18 Cl9 _ C20 :. Rate (kg/ha) 2.0 1.0 1.0 -r~----%~ %C %~ %C %~ ~C ~1~ %C
~: : Species : _ :
., Cotton 100 100 100 100 Soybean 100 : 0 20 80 Field Corn 100 70 100 50 Rice 90 80 60 : 30 Wheat 90 S0 40 10 Field Bindweed 100;: 80 80: 100 Morningglory~ 100 100 100 100 Velvetleaf~ ~ ~ 100 100 : ::100 1:00 Barnyardgrass: :100 100 100 100 Green Foxtail::: 100 100 100 100 Johnsongrass:~ : 100 90 :90 40 Yeil~ow Nut:se;dge ~100 ~90 ~ 80~ 10 ~: - ~. . :;. ,, ::. :; .
Table 7 (Cont.) Preemergence Herbicidal Activity Compound No. C21 C22 C23 C24 Rate (kg/ha) -r.-o~ . o 1 . o 1 . o ~K %C %K %C ~oK %C %K %C
Species _ _ Cot~on 100 100 30 40 Soybean ga 100 50 10 Field Corn 100 lO0 90 80 Rice 80 100 20 30 Wheat 100 100 70 0 Field Bindweed 100 100 100 90 Morningglory 100 100 100 100 Velvetleaf 100 100 100 90 Barnyardgrass 100 100 100 80 Green Foxtail 100 100 100 100 Johnsongrass 100 100 100 70 Yellow Nutsedge 80 100 40 30 , .
- Compound No. C25 C26 C32 C38 Rate (kg/ha) 2.0 1.0 1.0 1.0 : ~K %C %K ~C %K %C SK- %C
Species _ _ ~ :
: Cotton 100 100 100 90 Soybean 30 100 40 100 : Field Corn 70 100 20 100 ~ : Rice 60 90 50 100 :~. : Wheat 30 100 lO 100 ~`i : Field Bindwee:d ~ 100 100 100 : 100 : : Morningglory 100 100 100 : 100 : Velvetleaf 100 ~100 100 100 : Barnyardgrass 100 100 100 100 : Green Foxtail 90 100 80 100 : : Johnsongrass 70 100 80 100 Yellow Nutsedge 80 100 ~40 ND
Table 7 (Cont.) Preemergence Herbicidal Activit~
Compound No. C42 C43 C59 C69 Rate (kg/ha) 1.0 . i.0 1-0 0.5 %K ~ ~C %K %C %K %C %K %C
SDecies _ Cotton 90 100 100 40 Soybean 70 70 S0 10 Field Corn 40 70 70 30 Rice 60 90 80 30 Wheat 70 70 40 0 Field Bindweed100 100 lO0 90 ~orningglory 100 100 100 80 Velvetleaf 100 100 100 lO0 Barnyardgrass 100 100 100 20 Green Foxtail 100 100 100 20 Johnsongrass 60 95 100 40 Yellow Nutsedge 70 100 70 70 . .
.
Compound No. C70 C71 C72 C73 .
Rate (kg/ha) ---T~ r~~~ 1.0 1.0 %K %C ~ F %X %C %K %C
Species Cotton lO0 100 100 80 Soybean: 20 50 50 30 Field Corn 30 S0 : 60 30 Rice 70: 40 30 40 Wheat : :20 :40 20 ~ 50 FieId Bindweed 100 100 100 100 Morningglory 100 :I00 :100 100 Velvetleaf 100 100 lO0 100 Barnyardgrass 20 90; 100 90 Green Foxtail : 0 40 95 100 Johnsongrass: 80 ~ 60 90 80 Yell~ow Nutsedge 90 4060 20 "~
:: : :,: . ,.. :. . ,. - , , 666~
Table 7 (Cont.) Preemer~ence Herbicidal Activity Compound No. C74 C75 C76 C77 Rate (kg/ha) 1.0 _ l.0 1.0 1.0 %K 30C %~ %C %K ~C %X ~C
S~ecies ~ ~ ~
Cotton 100 90 60 95 Soybean 80 30 30 40 Field Corn 0 50 20 30 Rice 40 60 30 70 Wheat 30 40 20 60 Field Bindweed90 100 100 100 Morningglory 100 .lO0 100 100 Velvetleaf 100 100 100 100 Barnyardgrass 85 95 100 100 Green Foxtail 100 95 70 100 Johnsongrass 70 80 40 95 Yellow Nutsedge 20 30 30 30 Compound No. C78 C79 C80 C81. ~ :
Rate ~kg/ha) 1.0 ~ S-- 1.0~ - : 1 0 ~~~
Species _ %K ~.C %~ ~C ~ R~
Cotton 80 50 60 100 Soybean 40 : 0 20 100 Field Corn 30 10 0 50 Rice~ 50 50 20 50 Wheat ~ 40 20 30 100 Field Bindweed 100 80100: 100 Morningglory 100 100100 100 Velvetleaf 100 100100 100 Barnyardgra:ss : 100 ~ 80 95 100 Green:Foxtail ~ 90 100:100 100 Johnsongrass: 40 80 95 :100 Yellow Nutsedge 30 20 0 80 : :
~6~i~;6~
Table 7 (Cont.) Preemergence Herbicidal Activity Compound No. C82 C83 CB4 C85 Rate (kg/ha) 1.0 1.0 1.0 1.0 %K 7~C %K %C %K %C %K %C
S~ecies . .
Cotton 100 95 10 100 Soybean 10 95 0 30 Field Corn 20 20 10 95 Rice 30 40 20 80 Wheat 20 30 0 80 Field Bindweed 100 10030 100 Morningglory 100 100100 100 Velvetleaf ldO 100 90 100 Barnyardgrass 95 95 10 100 Green Foxtail 100 90 30 100 Johnsongrass 95 80 30 100 Yellow Nutsedge 10 20 ND ND
Compound No. . C86 - C87 C88C89 Rate (kg/ha) ~~~~ . 1.0 1.0 1.0 ~K %C ~R~ %K %C %K ~C
Species :: -Cotton 100 30 0 90 Soybean 70 20 10 30 Field Corn100 10 10 60 Rice 90 40 0 90 Wheat 90: 10 0 80 Field Bindweed 100 100 0 100 Morningglory 100: 100 0 100 Velvetleaf100 100 10 100 Barnyardgrass 100 95 40 100 Green Foxtail 100 0 O 100 Johnsongrass: - 100: : 30 10 95 Yellow Nutsedge ND ND ND ND
,: -: . : - , ... . .
Table 7 (Cont.) Preemergence_Herbicidal Activity Compound No. . C90 _C91 C92 C93 Rate (kg/ha) 1.0 1.0 1.0 1 0 %K %C %K__ ~C %K %C %K %C
Species _ _ _ Cotton 100 100 100 20 Soybean 100 90 30 0 Field Corn 80 80 20 30 Rice 80 90 40 50 Wheat 70 50 30 10 Field Bindweed 100 100 100 80 Morningglory 100 100 100 80 Ve.lvetleaf 100 100 100 100 Barnyardgrass 100 100 100 100 Green Foxtail 100 100 100 0 Johnsongrass 100 95 80 30 Yellow Nutsedge ND ND ND ND
.: .
, :~ Compound No. C94 C95 C97 C98 ~ Rate (kg/ha) 1.0 1.0 . I.0 0.5 :~ %K %C %K%C %K96C %~ ~C
:~' Species _ _ _ Cotton 80 100 100 100 ~' Soybean 20 60 20 30 : Field Corn 20 20 70 40 Rice 20 30 80 20 : Wheat 0: 10 70 20 ~ Field Bindweed 100 100 100 100 :~ : Morningglory 100 100 100 100 Velve~Iea:E 100 100 100 100 Barnyardgrass: 60 40 100~ 90 ~ Green Foxtail 50 50 100 80 : ~ Johnsongrass 60 60 90 95 : ~ Yellow Nutsedge ND ND ND ND
" ~ ~
6~i7 ~ 121 -Table 7 (Cont.) Preemergence Herbicidal Activity Compound No.C99 C100 C101 C102 Rate (kg/ha)0.5 0.5 0.~- 0.5 ~ %~ ~C ~K %C
Species_ Cotton 80 80 95 30 Soybean 70 S0 30 20 Field Corn 30 60 10 50 Rice 20 60 20 80 Wheat 10 20 10 50 Field Bindweed100 100 90 20 Morningglory100 100 100 80 Velvetleaf 100 100 100 100 Barnyardgrass10 70 60 100 Green Foxtail100 80 40 100 Johnsongrass 80 80 50 80 Yellow Nutsedge ND ND ND ND
.
- .
~ompound No. C103 C104_ C105 C106 Rate (kg/ha~ 0.5 0.5 ~ 0.~5 ~: 0.5 %K %C %K %C %~ %C %~ %C
Species ~
Cotton 30 30 100 100 Soybean ~ 10 10 95 ~ 90 Field Corn 30 90 70 30 Rice 50: 80 95 90 Wheat : 30 80 50 30 ~ield Bindweed40 100 100 100 Morningglory60: 90 lO0 100 Velvetl~af 100 100 100 100 Barnyardgrass : 95 95 100 : 100 Gree:n Foxtai~100 ~100 100 100 Johnsongra~s 80 ~ :95 lO0 100 YelIow Nutsedge ND : ::ND ~ ND ND
~266~$7 Table 7 (Cont.) Preemergence Herbicidal Activity Compound No. C107 C108 C109 CllO
Rate (kg/ha) 0.5 0.5 0.5 0.5 ~ F %K %C %~ %C ~oK ~ %C
SDecies Cotton 90 100 70 30 Soybean. 10 95 90 95 Field Corn 20 100 100 100 Rice 40 95 95 90 Wheat . 0 95 100 100 Field Bindweed 80 90. 95 100 Morningglory 95 100 100 100 Velvetleaf 100 100 100 100 Barnyardgrass 40 80 100 100 Green Foxtail 0 100 100 100 Johnsongrass 50 100 100 100 Yellow Nutsedge ND ND ND ND
~ .
: Compound No. Clll C112 C113 . C114 Rate (kg/ha) 0.5 0.5 ~~~-S~~ ~0.5 ~K ~'C %K _~OC %K ~C %K %C
': Species ; Cotton 20 9050 30 Soybean 40 40 0 0 ~ Field Corn 10 010 10 : : Rice 70 2020 . 20 Wheat 50 1010 10 Field:Bindweed 70 100 100 90 ~: Morningglory~ 70 90 90 95 : Velvetleaf 90 : 100 100 100 Barnyardgrass 100 40 50 70 : : Green Foxtail 100 80 30 70 ;~:: : Johnsongrass 70 95 30 70 Yellow Nutsedge :ND ND : ND ND
.. ~ . .: . .. ..... . .
~ - ~ . . : , - . . , ,,;; . . , , . : .. . . .
Table 7 (Cont.) Preemergence Herbicidal Activity CPmpound No. C115 C116 C117 C118 Rate (kg/ha) 0.5 0.5 0.5 0.5 %K _ _ C %X %C %K %C %K_ %C
Species _ _ Cotton 80 9S 50 20 Soybean 30 0 95 0 Field Corn 10 10 10 10 Rice 10 20 30 0 Wheat 30 10 0 10 Field Bindweed . 100 - 90 100 80 Morningglory 100 95 100 50 Velvetleaf 100 100 100 50 Barnyardgrass 50 80 40 10 Green Foxtail 90 40 80 10 Johnsongrass 90 80 20 10 Yellow NutsedgeND ND ND ND
Compound NO.Cll9 . .C120 C121 C122 Rate (kg/ha)~~~~~ O.S ~~0.5 ~ O S
--F~ -%R %C ~X %G ~ %C
Species _ ::
Cotton 50 70 95 70 Soybean 30 20 20 50 Field Corn 10 10 20 40 Rice 30 20 30 0 Wheat 30 10 10 ~10 Field Bindweed100 100 100 100 Morningg:lory100 ~ 90 90 ~ 80 Velve~leaf 100 100 lob loo Barnyardgrass 50 :80 70 70 Green Foxtail 0~ 0 20 50 Johnsongrass 70: 70 90 100 Yellow Nutsedge : ND ND : ND ND
~ :. .:.. - , : :
~26~i66~
Table 7 (Cont.) Preemergence Herbicidal Activity Compound No.C123 C124 C125 Rate (kg/ha)~~~1~ ~ ~ 0.5 0.5 %K _ %C ~ F %K %C
Species Cotton 50 20 20 Soybean S0 60 30 Field Corn 0 70 10 Rice 60 80 10 Wheat 10 60 lO
Field Bindweed 100 100 80 Morningglory 100 95 90 Velvetleaf 100 100 100 Barnyardgrass 100 100 30 Green Fox~ail 10 100 50 Johnsongrass 100 100 10 Yellow Nutsedge ND ND ND
,~
!
' ~,.
, :
': .
~ : 0833W30080Wmd~ ~
. :, ,-, : ~ , --:: -:: : ,~. ~. . .
. ~ .
.
Table 8 Postemergence Herblcidal Activity Compound No. 1 2 3 4 Rate.(kg/ha)_ 2.0 4.0 2.0 2.0 ~oK %C %~ %C %~ %C %X %C
Species _ _ ___ _ __ _ Cotton 100 100 100 90 Soybean 40 0 60 0 Field Corn 90 100 100 0 Rice 80 100 100 ~0 Wheat 10 100 90 90 Field Bindweed 100 100 lO0 100 Morningglory100 100 100 70 VelvetIea~ 100 100 ND 100 Barnyardgrass 100 100 100 90 Green Foxtail 100 100 ND ND
Johnsongrass 90 95 100 70 Yellow Nutsedge 50 50 100 0 Compound No. 6 7 8 9 Rate (kg/ha) 2.0 2.0 2.0 2.0 %~ %~ %K -~0-C %K %C %K %C
Species _ Cotton 100 90 100 100 Soybean 50 40 50 30 Field Corn100 40 30 100 Rice : lO0 : 80 90 70 Wheat 100 90 30 80 Field Bindweed 100 100 100 100 Morningglory 100 80 100 80 Velvetleaf 100 100 100 100 Barnyardgrass 100 100 100 100 Green Foxtail 100 100 100 100 Johnsongrass I00: 100 :70 80 Yellow:Nutsedge 100 :70 :30 80 ~6~i~7 Table 8 (Cont.) Postemergence Herbicidal Activity Compound No. 10 11 12 13 Rate (kg/ha) 2.0 2.0 2.0 2.0 ~oK %C %K %C %~ %C %X %C
Species ~
Cotton 100 100 100 70 Soybean 30 50 30 20 Field Corn 100 60 30 10 Rice 90 90 50 30 Wheat 100 90 70 20 Pield Bindweed 100 100 100 50 Morningglory 30 100 100 80 Velvetleaf 100 100 100 80 Barnyardgrass 90 100 100 80 Green Foxtail 100 100 100 40 Johnsongrass 80 80 90 30 Yellow Nutsedge 90 90 50 20 :
Compound No. 14 15_ 16 17 Rate tkg/ha) 1.0 1.0 ~.~ Z.0 %K %C %K %C %~ %C %~ %C
SDecies Cotton 100 100 100 100 Soybean 60 40 30 70 Field Corn 10 30 10 70 Rice : 30 90 30 30 Wheat 10 60 40 20 Pield Bindweed 100 100 90 90 Morningglory 100 100 100 100 Velvetleaf 100 :100 10'0 100 Barnyardgrass 100 100 100 70 Green Foxtail 90 100 100 20 Johnsongrass 80 90 80 70 Yellow Nutsedge 30 80 90 30 . : ~ ` " ' : ; ' . ' ',' " ' ' ' 6~7 Table 8 (Cont.) Postemergence Herbicidal Activity Compound No.18 19 20 21 Rate (kg/ha)0.5 2.0 0.5 2.0 %K _%C %K %C %~ %C %K %C-SDecies . _ _ Cotton 100 100 90 80 Soybean 30 40 40 20 Field Corn 60 50 30 20 Rice 20 50 20 30 Wheat 20 30 30 20 Field Bindweed 50 80 40 90 Morningglory 50 90 80 100 VelvetleaE 80 100 100 100 ~arnyardgrass 10 80 80 40 Green Foxtail 60 80 60 30 Johnsongrass 30 40 10 40 Yellow Nutsedge 10 90 10 30 Compound No. 51 52 Rate (kg/ha) . 2.a _ 0 ~oK ~ ~%C 30K %C
Species _ ~
Cotton 70 100 Soybean 50 95 Field Corn 10 100 Rice 30 90 Wheat: 10 100 Field Bindweed 90 : 100 Morningglory100 : 100 Velvetleaf 90 100 arnyardgrass70 I00 Green Poxta:il 10 100 Johnsongrass40 100 Yel~low Nutsedge 0 ~ ~ 100 ~z~
Table 8 (Cont.) Postemer~ence Herbicidal Activity Compound No............. Al A2~ A3 Rate (kg/ha) 4.~0 2.0 2.0 ~K %C %~ %C %K %C
SDecies .___ _ _ Cotton 100 90 100 Soybean 0 20 0 Field Corn 0 30 0 Rice 30 20 90 Wheat 30 30 80 Field Bindweed 100 80 100 Morningglory 100 70 60 Velvetleaf 100 ND 100 Barnyardgrass 100 90 100 Green Foxtail 100 ND ND
Johnsongrass 75 60 95 Yellow Nutsedge 0 10 0 -.~: .
: Compound No. A4 A6 Bl B2 - Rate (kg/ha) 1.0 0.5 2.0 ~ r---%K %C %K %C %~ %C %K %C
Species _ ~
:
Cotton 100 90 100 100 : : Soybean 40 20 10 30 ~ Field Corn 40 20 40 30 .: : : Rice 20 30 50 80 ~heat 90 90 100 100 Field Bindweed90 10 100 100 : Morningglory100 90 100 40 : Velvetleaf 100 ~ 100 100 100 : Barnyardgrass100 100 100 100 Green Foxtail100 90 100 100 Johnsongrass 60 30 80 80 Yellow Nutsedge 100 : 50 40 80 ~: . .
~:: ~ : . - ., . : - , - 1 2g -Table 8 (Cont.) Postemergence Herbicidal Activity Compound No. B3 B4 B5 _ B6 Rate (kg/ha) ~ 2.0 1.0 2. 1.0~~~~~
%K ~C %X %C %K %C ~ %C
Species Cotton 100 100 100 100 Soybean 30 40 60 60 Field Corn 70 30 Z0 100 Rice 90 90 80 100 Wheat 90 100 90 100 Field Bindweed 100 100 100 90 Morningglory80 90 100 100 Velvetleaf 100 100 100 100 Barnyardgrass 100 100 100 100 Green Foxtail 100 100 100 100 Johnsongrass90 80 90 80 Yellow Nutsedge 30 90 60 100 ;
.
Compound-No. B7 B8 B10 Bll Rate (kg/ha)1.0 2.0 1.0 1.0 : %K %C %K ~ %C %K %C %~ %C
Species ~ ~
~ Cotton ~ 100 100 100 100 : : : Soybean 60 80 20 30 ~:~ Field Corn 100 70 0 0 ~: - Rice : 100 100 20 30 Wheat 100 100 10 100 : Field Bindweed 100 100 100 100 Morningglory 100 100 100 100 Yelvetleaf: 100 100 100 100 : Barnyardgrass 100 100 I00 : 100 Greèn Foxtail 100 100 100 100 Johnsongrass : : 80 :70 90 90 :Yellow Nutsedge 80 : 70 ~ 20 : 100 Table 8 (Cont.) Postemergence Herbicidal Activity Compound No.B12 B13_ B14 B15 Rate (kg/ha) 1;.0 l.0 1.0 2.0 ~ %K %C %K ~C
Species ~
Cotton 100 100 100 100 Soybean 30 .100 90 80 Field Corn 10 60 .20 60 Rice 20 50 80 90 Wheat 100 90 80 100 Field Bindweed100 100 90 100 Morningglory 100 lbO 90 lO0 Velvetleaf lO0 lO0 100 lO0 Barnyardgrass 100 lO0 100 100 Green Foxtail 100 lO0 100 lO0 Johnsongrass 30 lO0 60 lO0 Yellow Nutsedge90 100 70 90 .
:. .
, .
: Compound No.B16 B17 B18 ,B21 . Rate (kg/ha)1.0 1.0 2Ø 1.0 %~ %C %K %C %~ %C %K ~C
Species :: :
~ Cotton lO0 lO0 100 lO0 :~ Soybean 4a 40 50 30 Field Corn 30 30 20 30 : Rice 50 30 90 20 ~ Wheat 100 40 70 lO0 : : : Field BindweedlO0 lO0 lO0 lO0 Morningglory 80 90 lO0 lO0 Velvetleaf lO0 100 100 90 :Barnyardgrass100 70 lO0 lO0 Green FoxtaillO0 100 100 100 Johnsongrass 40 30 40 lO
: Yellow Nutsedge 100 : 60 90 80 ~: :
, ~
~, . , ~.: : .:... . .. ,.... ... . . -: . . . . . . .
~ :~ . ... . . . .
i$~
Table 8 (Cont.) Postemergence Herbiciclal Activity Compound No B22 B23 B25 B30 Ra-te (kg/haj~ - 1.0 1.0 b. 5 %~ %C ~K %~ %~ %C %K %C
Species _ ~
Cotton 30 100 80 80 Soybean 30 10 30 10 Field Corn 20 40 90 10 Rice 70 90 50 70 Wheat 90 80 90 100 Field Bindweed 50 100 lO0 50 Morningglory100 100 100 100 VelYetleaf 100 100 100 100 Barnyardgrass 100 60 100 100 Green Foxtail 100 100 100 100 Johnsongrass10 100 50 10 Yellow Nutsedge 10 90 90 10 .
Compound No.B31 B32 _B33 B50 Rate (kg/ha)1.0 O.S 1.0 o.5 %C ~ F %K %C %~ %C
Species Cotton 100 100 100 : 100 Soybean 20 10 30 30 Field Corn 40 0 40 20 Rice 40 20 40 40 Wheat 80 70 100 40 Field Bindweed 100 80 100 70 Morningglory90 100 100 100 Velvetleaf 90 100 100 100 Barnyardgrass 100 100 100 100 Green Foxtail 100 100 100 100 Johnsongrass50 0 40 :30 Yellow Nutse~dge 90: 0 :60 20 , :
, ~ , . ... ~ ... , - -~- ,, , ,, , :
.
. " . . :, - :: .. -: - : .;, ,- :: :
~6~i67 Table 8 (Cont.) Postemergence Herbicidal Activity Compound No. B57 Cl Rate (kgtha) 0.5 2.0 %K %~ %K ~C
SDecies .
Cotton 100 100 Soybean 30 30 ~ield Corn 30 70 Rice 90 20 Wheat 90 0 Field Bindweed80 100 Morningglory 100 100 Velvetleaf 100 100 Barnyardgrass 100 100 Green Foxtail 100 100 Johnsongrass 40 80 Yellow Nutsedge 60 60 : :
~: :
:~ .
` Compound No. . C2 C3: C4 C5 :: Rate (kg/ha) 1.0 2.0 , 2.0 2.0 %K %C %K %C %K %C
SDecies ;: . . - _ Cotton 100 100 70 100 Soybean 90 40 40 90 Field Corn 100 100 40 100 Rice : 100 70 50 100 Wheat100 40 30 100 Field Bindweed100 90 100 : 100 orningglory 100 100 90 100 Velvetleaf : 100 100100 100 Barnyardgrass 100 100 90 100 Green Foxtail 100 : 100 90 100 Johnsongrass 100 : 90 40 90 Yel~low Nutsedge 100 :30 20 100 , .,, ~, ~ ,., , ,, . , ~ . . , ~ ~ :: - . , . . .. . .. ..
- . . . . .
.~: ~ ~ : .. , . : , i7 Table 8 ~Cont.) Postemer~n_ _Herbi idal Activity Compound No. . C6 C7 C8 C9 Rate (kg/ha) 2.~ 1.0 2.0 1.0 %K %C %~ %C ~K %C %K %C
SDecies _ Cotton 100 100 100 90 Soybean 90 - 60 90 80 Field Corn 100 50 90 80 Rice 100 80 80 50 Wheat 100 10 80 60 Field-Bindweed 100 100 100 90 Morningglory 100 100 100 80 Velvetleaf 100 100 100 100 Barnyardgrass 100 100 60 100 Green Foxtail 100 100 100 100 Johnsongrass 100 90 80 90 Yellow Nutsedge 100 80 60 20 : ~
Compound No. C10 Cll Ci2 . C13 Rate (kg/ha) 1.0 1.0 1 2.0 %K~ %C %K %C %X %C %K %C
Species ~ ~
Cotton 100 100 100 100 Soybean 100 ~ 90 90 80 Field Corn 60 100 100 100 Rice 60 100 100 100 Wheat 60 100 100 100 Field Bindweed 60 ::90 100 ~ lQ0 Mo~ningglory : 100 100 100 100 Velvetleaf 100 : 100 100 100 Barnyardgrass 100 100 I00 100:
:Green:Foxtail 100 100 : 100 100 Johnsongrass: :80 90 100 100 Yellow:Nutsedge 10 100 100 ~ 100 i66~7 - 13~ -Table 8 (Cont ) Postemergence Herbicidal Activity Compound No. C14 Cl5 C16 C17 Rate (kg/ha) 2Ø Z.0 2.0 2.0 - %K %C %K ~C %K %C %~ %C
~ ~T _ ___ _______ r Cotton100100100 lO0 Soybean100 90 100 100 Field Corn100 90 100 100 Rice 70 5090 100 Wheat100 lO0100 100 Field Bindweed 100 100 100 90 Morningglory100 100 100 100 Velvetleaf100 100 100 100 Barnyardgrass 100 100 100 100 Green Foxtail 100 100 100 100 Johnsongrass100 90 100 50 Yellow Nutsedge 100 90 100 100 .
.~ .
Compound No. C18 Cl9 C20- C21 : ................. Rate (kg/ha) 1Ø1.0`- 1 0 1.0 : :................ %K - %C %K %C ~K~ C %X ~C
Svecies _ . _ : Cotton 100 100 100 100 Soybean 40 40 100 lO0 Field Corn 30 : Z0 0 100 :~ Rice 10 10 20 60 ;: Wheat 100 100 100 lO0 `` Field Bindweed 100 100 100 100 Morningglory 100 100 100 100 `~ Velyetleaf 100 100 lO0 100 ~ Barnyardgrass lO0 100 100 100 -~:- 5reen Foxtail 100 100 100 100 Johnsongrass 90 100 40 100 :Yellow Nutsed:ge 100 60 10 80 , ~
.:..
~ ~:
:~:: ~ :
:~;~: :
: : . ...
.
~2~
Table 8 (Cont.) Postemer~ence Herbicidal Activity Compound No. C22 C23 C24 C25 Rate (kg/ha) 1.0 ~ 1.0 2.0 %K %C %K %C %K %C %K %C
SD ecies ~ -_ _ , _ _ Cotton 100 100 50 100 Soybean lO0 80 20 70 Field CornlO0 80 20 60 Rice 80 30 lO 50 Wheat 100 90 10 60 Field Bindweed 100 100 100 100 Morningglory100 80 90 100 VelvetleaflO0 lO0 100 100 Barnyardgrass lO0 100 80 lO0 Green Foxtail lO0 lO0 lO0 100 Johnsongrass100 100 60 100 Yellow Nutsedge 80 40 0 70 .
:
~: , . . .
Compound No. C26 C32 C38 .
Rate (kg/ha)I.0 l.0 : ~ 1.0 ~: ~R~ g~ %K %C %K %C
sPecies ' ' ~ ~
:~ Cotton 100 lO0 lO0 ~: Soybean 80 80 lO0 Field CornlO0 20 lO0 Rice 90 50 lO0 ~ Wheat 90 50 100 :G : Field Rindweed l:00 lO0 70 Morningglory: 100lO0 lO0 Velvetleaf100 lO0 1:00 Barnyardgrass 100 100 100 : : Green Foxtail 100 80 100 : Johnsongrass90 40 90 Yellow:~utsedge 90 20 ND
.. , : : ~
Table 8 (Cont.) Postemergence Herbicidal Activity Compound No. C42 C43 C59 _ C69 Rate (kg/ha) ~---r~r-~ ---r~r~- ~K %C %K %C .
Species _ . .
Cotton 100 100 lO0 lO0 Soybean 100 90 80 50 Field Corn 100 100 80 80 Rice 60 50 40 60 Wheat 90 95 80 90 Field Bindweed 100 100 100 100 Morningglory 95 .100 100 100 Velvetleaf 100 100 100 100 Barnyardgrass 95 100 100 100 Green Foxtail 100 100 100 50 Johnsongrass 95 100 95 60 Yellow Nutsedge40 95 100 50 : .
. . . .
: Compound No. C70 C71 . C72 C73 : Rate (kg/ha) 1.~ 1.0 1.0 1.0 %K ~ %C 30~ ~ %C %K %C
Species : : : Cotton 90 100 100 100 Soybean 60 60 70 : :85 :.~ Field Corn 40 60 50 30 :Rice 30 40 60 60 : : :Wheat 40 95 30 80 : Field Bindweed 100 :100 100 100 Morningglory lO0 100 : 100 : 100 Velvetlea~ 100 : 100 : 100 100 : : Barnyardgrass1:00:~ 100 100 90 ~ Green~Foxta:il 30 100 : 60 ~ 90 7~ : Johnsongrass 70 50 50 70 ~ Yéllow Nutsedge 40 : 20 ~ :60 30 ~6~;~7 Table 8 (Cont.) Postemergence Herbicidal Activit~
Compound No. C74 C75 C76 C77 Rate (kg/ha) 1.0 1.0 1.0 1.0 %K O~C ~ %K %C %K %C
: S Dec i e s ~ . . _ ~
Cotton 85 95 95 100 Soybean 90 90 80 80 Field Corn 40 100 70 100 Rice 60 40 40 30 Wheat S0 40 30 100 Field Bindweed 95 100 -100 100 Morningglory100 100 95 100 Velvetleaf100 100 100 100 Barnyardgrass 100 95 95 95 Green Foxtail 85 100 95 100 Johnsongrass50 80 40 70 Yellow Nutsedge 30 10 20 30 . .
Co~pound No. C78 C79 C80 C81 Rate (kg/ha) ~ 1.0~~~.0 1.0: 1.0 %~ %C %K %C %K ~C %K %C
Species . .
Cotton 100 100 100 100 Soybean 100 50 80 100 Field Corn 100: 20 40 80 Rice 30 20 10 90 Wheat 90 40 40 95 Field Bindweed 100 50 100 100 Morningglory 100 60 100 100 VelYetleaf 100 100 100 100 Barnyardgrass 100 100 40 100 Green Foxtail 90 95 100 100 Johnsongrass 60 80 40 100 Yellow Nutsedge 20 70 20 20 : : :
~ :
,.: ~ :
. r ,: ' ' ` ' . ` `' ,.,. "'''. . ' ','' ' . " .`'' `
' ~ : "' : '' ", ' ' '' . ~,,:' ;~2~i6;6~
Table 8 (Cont.) Postemergence Herbicidal Activity Compound No.C82 C83 C84 C85 Rate (kg/ha)~~~~~~ ~ 1.0 1.0 1.0 ~o ~ % C % ~ % C % ~ % C ~ol~ % C
SDecies Cotton 100 100 80 100 Soybean 80 100 40 90 Field Corn 100 95 40 95 Rice 70 60 20 95 Wheat 90 90 30 80 Field Bindweed 100 .100 20 95 Morningglory100 100 90 100 Velvetleaf 100 100 100 100 Barnyardgrass 100 10095 100 Green Foxtail 100 10030 100 Johnsongrass 100 95 20 90 Yellow Nutsedge 0 60 ND ND
, .
. . .
Compound No. C86 C87 C88. C89 Rate (kg/ha) 2.0 ~ 1.0 1.0 ------~~K %C %K: %C
Species Cotton 100 90 10 90 Soybean 80 100 30 90 Field Corn 100 100 20 100 Rice 100 50 10 70 Wheat : 100 60 I0 100 Field Bindweed~ 100 100 10 95 Morningglory 100 100 20 100 Velvetleaf - 100 100 20 lO0 Barnyardgrass : 100 100 20 100 Green Foxtail 100 80 50 100 Johnsongras:s 100 30 30 80 Yellow:Nutsedge ND~ ND ND ND
.. . .. . . . ~ . . . . . ... .. . . .
66~7 Table 8 (Cont.) Postemergence Herbicidal Activity Compound No. C90 C91 C92 _C93 Rate (kg/ha) 1.0 1.0 1.0 1.0 %K %C %K %C %~ %C %~ %C
Species ~_ _ Cotton 100 100 100 100 Soybean 100 100 90 70 Field Corn 95 100 100 70 Rice 60 90 70 30 Wheat 100 100 80 80 Field Bindweed 100 100 100 70 Morningglory 100 100 100 95 Velvetleaf 100 lO0 100 100 Barnyardgrass 100 lO0 100 100 Green Foxtail 100 100 80 95 Johnsongrass 100 100 70 30 Yellow Nutsedge ND ND ND ND
Compound No. C94 C95. C97- C98 Rate (kg/ha) 1.0 1.0 l.0 0.5 %K %C %K %C %K %C %K %C
S~ecies Cotton 100 100 95 90 Soybean 80 95 95 70 Field Corn 50 95 lO0 70 Rice ~ 30 70 95 70 Wheat 40 100 100 90 Field Bindweed 95 100 95 100 Morningglbry 100 lO0 100 l00 Velvetleaf lO0 100 100 100 Barnyardgrass 80 90 95 95 Green Fox~tail 95 100 lO0 70 Johnsongrass 60 70 95 90 Yellow Nutsedge ND ND ND ~ ND
: . ~
.....
~: ,. , ~, - : , -: , : -Table 8 (Cont.) Postemergen_ _Herbicidal Activit~
Compound No. C99 C100 C101 C102 Rate (kg/ha) 0.5 0.5 0.5 0.5 %K ~C %K %C %K %C %K %C
Specles Cotton 90 100 100 100 Soybean 100 100 60 50 Field Corn 100 100 50 60 Rice 40 40 20 70 Wheat 100 100 40 95 Field Bindweed 100 100 90 90 Morningglory 100 100 90 100 Velvetleaf 100 100 100 95 Barnyardgrass 100 100 30 60 Green Foxtail 90 100 10 100 Johnsongrass 100 90 50 70 Yellow Nutsedge ND ND ND ND
. ' . . .
Compound No. ~ C103. C104 C105 C1.06 Rate (kg/ha) 0.5 0.~ 0.5 0.5 ~o~ R~ %~ %C %K %C
S~ecies ~
Cotton 100 80 100 100 Soybean 30 80 100 100 Field Corn 30 90 95 100 Rice 40 70 95 95 Wheat 30 90 1:00 100 Fi:eld:Bindweed 95 50 100 : 100 Morningglory 95 90 100 100 Velvet:leaf 100 100 100 100 Barnyardgrass 60 95 100 100 Green Foxtail 100 9S 100 100 Johns:ongrass 70 80 100 100 Yellow Nutsedge ND ~ ND ND ND
~. :. ., : , . .
6q:~7 Table 8 (Cont.) Postemergence Herbicidal Activity Compound No. Cl07 C108 C109 CllO
Rate (kg/ha) 0.5 0.5 0 5 0.5 -~Rr~ K %C %K %C %K %C_ Species Cotton 100 100 95 80 Soybean 60 100 95 100 Field Corn 60 100 80 90 Rice 20 95 80 80 Wheat 20 100 95 95 Field Bindweed 100 100 100 100 Morningglory 100 100 100 100 Velvetleaf 100 100 lO0 100 Barnyardgrass95 100 100 100 Green Foxtail90 100 100 100 Johnsongrass 60 100 100 100 Yellow Nutsedge ND ND ND ND
.. ..
.
... . . .
Compound No.Clll Cl12 C113 C114 .
:: Rate (kg/ha) 0.5 0.5 0.5 `0.5~~
. %K _ %C ~K %C ~K %C %~ %C
:~-, S DeC i e s :::, Cotton 40 90 80 95 Soybean 50 90 40 50 ~ Field Corn 20 : 40 30 30 :~: : Rice 20 20 30 80 ~: Wheat 70 90 30 30 Field Bindweed 60 : 100 100 lO0 ,m - ~ Morningglory 100 lO0 lO0 100 :~ Velvetleaf100 ~ 100 100 lO0 Barnyardgrass 100 9:5 30 70 :: ~ Green Foxtail 100 ~ lO0 80 90 : Johnsongrass ~::95 95 40 30 Yellow Nutsedge ND ND ND ND
~:: : - ,, . : : , ,~ , . :
Table 8 (Cont.) Poste er~ence Herbicidal Ac_ivity Compound No. C115 C116 C117 C118 Rate (kg/ha) 0.5 0~ O.S 0.5 ~ K %C %K %C %K %C %~ %C
Species . . _ _ _ _ _ Cotton 20 100 100 40 Soybean 30 60 100 95 Field Corn 30 40 100 100 Rice 10 20 0 10 Wheat 30 60 95 60 Field Bindweed 10 80 100 95 Morningglory 30 100 100 80 Velvetleaf 20 100 lO0 100 Barnyardgrass 20 70 100 60 Green Foxtail 30 70 100 40 Johnsongrass - 30 80 70 20 Yellow Nutsedge ND ND ND . ND
Compound No. Cll~ C120 C121 C122~ . :
Rate (kg/ha) 0.5 ~ S~- 0.5 0.5 %K ~C %K ~C %K %C
Species _ _ -Cotton 95 80 100 95 Soybean 95 95 80 80 Field Corn 40 60 10 60 Rice 10 10 20 10 ~heat : 90 100 100 100 Fie}d Bindweed 100 100 100 95:
Morningglory: 100 : 100 , 100 100 Velvetleaf 100 100 100 100 Barnya:rdgrass 50 50 80 100 Green Foxtail 70: 20 30 80 Johnsongrass ~ 60 40 : 80 80 Yellow Nutsedge ND ND ND: ND
:~......... . :- ,, ,; ~ :
~;: : : , ~ , ; . , :: ~ ,..-: :
;6~7 Table 8 (Cont.) Postemergenc _Herbicidal Activ_ty Compound No. C123 C124_ C125 Rate (kg/ha) 0.25 0.5 -~~ 5 % K % C % X% C % K% C
Species Cotton 100 100 100 Soybean 100 100 100 Field Corn 90 100 100 Rice 90 70 Wheat 100 100 100 Field Bindweed 100 100 100 Morningglory 100 100 100 - Velvetleaf 100 100 100 Barnyardgrass 95 100 95 Green Foxtail 95 100 95 Johnsongrass 95 95 90 Yellow Nutsedge ND ND ND
: . :
; .
:
: ~: : . :
:
~ 08~33W30080Wmd~
Claims (22)
l. An herbicidal compound of the formula:
in which R3 is an alkylene radical or a fluoroalkylene radical;
R11 is -N(R6)(R7), -OR4, -ZR10, or -OR9;
R6 and R7 are independently selected from hyd-rogen, alkyl, alkenyl, alkynyl, cycloalkyl, aryl, alkoxy, alkylsulfonyl, cycloalkylsul-fonyl, arylsulfonyl, aralkylsulfonyl, aminosulfonyl, alkylaminosulfonyl, dialkyl-aminosulfonyl, alkenylsulfonyl, phenylalke-nylsulfonyl, and any of the foregoing radi-cals carrying one or more substituents sel-ected from halogen, nitro, amino, alkoxy, alkyl, haloalkoxy, alkenyloxy, haloalkenyl-oxy, alkoxyalkoxy, alkoxyalkylthio, cyano, aminocarbonyloxy, alkylaminocarbonyloxy, dialkylaminocarbonyloxy, acylamino, alkoxy-carbonyl, aminocarbonyl, alkylaminocarbo-nyl, dialkylaminocarbonyl, and hydroxycar-bonyl, with the proviso that when one of R6 and R7 is connected to the nitrogen atom of -N(R6)(R7) by an oxygen or sulfur atom, then the other of R6 and R7 is hydrogen or a radical that is connected to the nitrogen of -N(R6)(R7) by a carbon-nitrogen linkage, or R6 and R7 taken together with the nitro-gen atom to which they are attached form a pyrrolidino, piperidino, morpholino or thiazolidino ring which is unsubstituted or substituted with a carboxylic acid ester or amide substituent;
R4 is hydrogen or alkyl;
Z is O or S;
R10 is alkyl (which is substituted with one or more substituents selected from the group consisting of nitro, halogen, furyl, tetra-hydrofuryl, acetyl, aminocarbonyl, alkylam-inocarbonyl, dialkylaminocarbonyl, cyano, alkoxycarbonyl, alkylamino, dialkylamino, alkoxy, alkylthio, alkylsulfinyl, alkylsul-fonyl, phenyl, phenoxy, phenylthio, phenyl-sulfinyl, and phenylsulfonyl wherein any phenyl group or the phenyl portion of any phenyl-containing group is unsubstituted or substituted with one or more substituents selected from alkyl, haloalkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, halogen, cyano, nitro, hydroxy, amino, al-kylamino, dialkylamino, and hydroxycarbo-nyl), alkenyl, alkynyl, or a cyclic radi-cal selected from the group consisting of tetrahydrofuranyl, 2-oxotetrahydrofuranyl, tetrahydrothiophenyl, 1-oxotetrahydrothio-phenyl, 1,1-dioxotetrahydrothiophenyl, cyc-lohexyl, pyridinyl, naphthyl, 2,2-dimethyl-3,4-dihydrobenzofuranyl, phenyl, or phenyl substituted with methylthio, nitro, chloro, or methyl;
R9 is a group of the formula -N=C(alkyl)(alkyl) or -N=C(S-alkyl)(alkyl);
X is Br, Cl, F, or haloalkyl;
Y is bromine, chlorine, fluorine, methyl, haloalkyl, or a radical of the formula R8OCH2-, R8SCH2-, R8SOCH2- or R8SO2CH2-where R8 is C1-C3alkyl, C2-C5alkenyl, or C3-C5alkynyl, phenyl, or phenyl substituted with halogen, alkyl, or haloalkyl;
R1 is halogen, alkyl, haloalkyl, alkoxyalkyl, cyanoalkyl, arylalkyl, alkylthio, alkylsul-finyl, alkylsulfonyl, alkylthioalkyl, al-kylsulfinylalkyl or alkylsulfonylalkyl; and (a) where R11 is -N(R6)(R7), -ZR10, or -OR9, R2 is alkyl, haloalkyl, alkenyl of 2 to 5 carbon atoms, alkynyl of 3 to 5 carbon atoms, cyano-alkyl, thiocyanoalkyl or a group of the formula -alkylene-Y1-R5 in which said alkylene group has
1 to 5 carbon atoms, Y1 is being oxygen or S(O)r in which r is 0 to 2, and R5 being alkyl, alke-nyl of 2 to 5 carbon atoms or alkynyl of 3 to 5 carbon atoms; and (b) where R11 is -OR4, R2 is CHF2 or CH2F;
or a base addition salt of the compound in which R4 is hydrogen or in which one of R6 and R7 is hydrogen and the other of R6 and R7 is arylsulfonyl or a sub-stituted or unsubstituted alkylsulfonyl or alkenyl-sulfonyl.
or a base addition salt of the compound in which R4 is hydrogen or in which one of R6 and R7 is hydrogen and the other of R6 and R7 is arylsulfonyl or a sub-stituted or unsubstituted alkylsulfonyl or alkenyl-sulfonyl.
2. The herbicidal compound of claim 1 in which R4 is hydrogen.
3. The herbicidal compound of claim 2 in which X is fluorine.
4. The herbicidal compound of claim 3 in which R1 is methyl.
5. The herbicidal compound of claim 4 in which R3 is -CH2- or -CH(CH3)-.
6. The herbicidal compound of claim 5 in which Y is chlorine.
7. The herbicidal compound of claim 6 in which R2 is halomethyl.
8. The herbicidal compound of claim 7 in which R2 is -CHF2.
9. The herbicidal compound of claim 8 in which R11 is -N(R6)(R7).
10. The herbicidal compound of claim 9 in which at least one of R6 and R7 contains a sulfonyl moiety.
11. The herbicidal compound of claim 10 in which one of R6 and R7 is an arylsulfonyl group.
12. The herbicidal compound of claim 11 in which one of R6 and R7 is a phenylsulfonyl group which is substituted with halogen, alkoxy, or alkyl.
13. The herbicidal compound of claim 8 in which R11 is -ZR10.
14. The herbicidal compound of claim 13 in which Z is an oxygen atom.
15. The herbicidal compound of claim 14 in which R10 is a substituted alkyl group.
16. The herbicidal compound of claim 15 in which the substituent on the alkyl group is halogen, cyano, phenyl, substituted phenyl, alkoxy, alkylthio, or alkoxycarbonyl.
17. The herbicidal compound of claim 16 in which the substituent on the alkyl group is halogen, alkoxy, or alkoxycarbonyl.
18. The herbicidal compound of claim 8 in which R11 is -OR9.
19. A base addition salt of the herbicidal com-pound of claim 8 in which R11 is -OR4.
20. A base addition salt of the herbicidal com-pound of claim 8 in which R11 is -N(R6)(R7) and one of R6 and R7 is hydrogen and the other is arylsulfo-nyl or a substituted or unsubstituted alkylsulfonyl or alkenylsulfonyl.
21. An herbicidal composition comprising an herbicidally effective amount of a compound of claim 1 in admixture with a suitable carrier.
22. A method for controlling undesired plant growth which comprises applying to the locus where control is desired an herbicidally effective amount of the composition of claim 21.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000493598A CA1266667A (en) | 1984-10-31 | 1985-10-22 | Herbicidal aryl triazolinones |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US66693384A | 1984-10-31 | 1984-10-31 | |
| US666,933 | 1984-10-31 | ||
| CA000493598A CA1266667A (en) | 1984-10-31 | 1985-10-22 | Herbicidal aryl triazolinones |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA1266667C CA1266667C (en) | 1990-03-13 |
| CA1266667A true CA1266667A (en) | 1990-03-13 |
Family
ID=24676118
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000493598A Expired - Lifetime CA1266667A (en) | 1984-10-31 | 1985-10-22 | Herbicidal aryl triazolinones |
Country Status (11)
| Country | Link |
|---|---|
| EP (1) | EP0199794A4 (en) |
| JP (1) | JPS61501991A (en) |
| KR (1) | KR880001297B1 (en) |
| CN (1) | CN85108193A (en) |
| AU (2) | AU573930B2 (en) |
| BR (1) | BR8507017A (en) |
| CA (1) | CA1266667A (en) |
| HU (1) | HUT41611A (en) |
| IL (1) | IL76857A0 (en) |
| RO (1) | RO96607A (en) |
| WO (1) | WO1986002642A1 (en) |
Families Citing this family (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4743291A (en) * | 1984-10-31 | 1988-05-10 | Fmc Corporation | Herbicidal aryl triazolinones |
| AU572739B2 (en) * | 1985-10-26 | 1988-05-12 | Nihon Nohyaku Co., Ltd. | 1,2,4-triazolin-5-one derivatives |
| JPS6299368A (en) * | 1985-10-26 | 1987-05-08 | Nippon Nohyaku Co Ltd | Delta2-1,2,4-triazolin-5-one derivative production and use thereof |
| US4846875A (en) * | 1987-07-21 | 1989-07-11 | Fmc Corporation | Herbicidal triazolinones |
| EP0354622A1 (en) * | 1988-08-11 | 1990-02-14 | Shell Internationale Researchmaatschappij B.V. | Oxadiazolone herbicides |
| UA26918C2 (en) | 1988-08-31 | 1999-12-29 | Фмк Корпорейшн | Triazolinone derivative exhibiting herbicidal activity, herbicidal composition, method for inhibition of weed growth |
| CA1331463C (en) * | 1988-08-31 | 1994-08-16 | Kathleen Megan Poss | Herbicidal triazolinones |
| US4985065A (en) * | 1989-05-10 | 1991-01-15 | Fmc Corporation | Tetrazolinone herbicides |
| JPH05208975A (en) * | 1991-12-02 | 1993-08-20 | Mitsubishi Kasei Corp | Tetrahydrofuran derivative and herbicide comprising the same as active ingredient |
| DE19802697A1 (en) | 1998-01-24 | 1999-07-29 | Bayer Ag | Selective, synergistic herbicidal composition, especially for weed control in wheat |
| US6492527B1 (en) * | 1999-10-13 | 2002-12-10 | Fmc Corporation | Process to prepare aryltriazolinones and novel intermediates thereto |
| WO2003029226A1 (en) * | 2001-09-26 | 2003-04-10 | Basf Aktiengesellschaft | Heterocyclyl substituted phenoxyalkyl-, phenylthioalkyl-, phenylaminoalkyl- and phenylalkyl-sulfamoylcarboxamides |
| EP1663204B1 (en) | 2003-08-29 | 2014-05-07 | Exelixis, Inc. | C-kit modulators and methods of use |
| KR101256139B1 (en) * | 2009-01-05 | 2013-04-23 | 동부대우전자 주식회사 | Throwing device of detergent for auto washer |
| KR101256138B1 (en) * | 2009-01-05 | 2013-04-23 | 동부대우전자 주식회사 | Throwing device of detergent for auto washer |
| CN103493822B (en) * | 2013-09-05 | 2015-12-02 | 江苏东宝农化股份有限公司 | There is the weed killer herbicide of broad spectrum weeding function |
| CN103493821B (en) * | 2013-09-05 | 2015-12-02 | 江苏东宝农化股份有限公司 | A kind of weed killer herbicide with wide-spectrum synergy herbicide effect |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US404019A (en) * | 1889-05-28 | Pessary | ||
| US3922162A (en) * | 1974-03-28 | 1975-11-25 | Velsicol Chemical Corp | 2-Alkyl-4-aryl-1,2,4-triazolidin-3-ones |
| US4318731A (en) * | 1979-08-25 | 1982-03-09 | Nihon Nohyaku Co., Ltd. | Δ2 -1,2,4-triazolin-5-one derivatives and herbicidal usage thereof |
| JPS5653662A (en) * | 1979-10-08 | 1981-05-13 | Nippon Nohyaku Co Ltd | Preparation of delta2-1,2,4-triazolin-5-ones |
| CH651029A5 (en) * | 1980-12-25 | 1985-08-30 | Nihon Nohyaku Co Ltd | TRIAZOLINE DERIVATIVES, METHOD FOR THE PRODUCTION THEREOF AND HERBICIDES CONTAINING IT. |
| AU3507784A (en) * | 1983-10-13 | 1985-05-07 | Fmc Corporation | Herbicidal |
| BR8506209A (en) * | 1984-03-29 | 1986-04-15 | Fmc Corp | 1-ARIL-DELTA2-1,2,4-TRIAZOLIN-5-ONAS HERBICIDES |
| CA1242730A (en) * | 1984-05-31 | 1988-10-04 | Atsushi Tsushima | .delta..SUP.2-1,2,4-TRIAZOLIN-5-ONE DERIVATIVES AND HERBICIDAL COMPOSITIONS CONTAINING THE SAME |
-
1985
- 1985-10-21 HU HU855073A patent/HUT41611A/en unknown
- 1985-10-21 EP EP19850905564 patent/EP0199794A4/en not_active Withdrawn
- 1985-10-21 BR BR8507017A patent/BR8507017A/en unknown
- 1985-10-21 JP JP60504935A patent/JPS61501991A/en active Pending
- 1985-10-21 KR KR1019860700409A patent/KR880001297B1/en active IP Right Grant
- 1985-10-21 AU AU50663/85A patent/AU573930B2/en not_active Expired - Fee Related
- 1985-10-21 WO PCT/US1985/002065 patent/WO1986002642A1/en not_active Application Discontinuation
- 1985-10-22 CA CA000493598A patent/CA1266667A/en not_active Expired - Lifetime
- 1985-10-28 IL IL76857A patent/IL76857A0/en unknown
- 1985-10-30 CN CN198585108193A patent/CN85108193A/en active Pending
-
1986
- 1986-06-28 RO RO86123925A patent/RO96607A/en unknown
-
1988
- 1988-03-18 AU AU13339/88A patent/AU1333988A/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| BR8507017A (en) | 1987-01-06 |
| AU5066385A (en) | 1986-05-15 |
| IL76857A0 (en) | 1986-02-28 |
| KR880001297B1 (en) | 1988-07-22 |
| CA1266667C (en) | 1990-03-13 |
| JPS61501991A (en) | 1986-09-11 |
| EP0199794A1 (en) | 1986-11-05 |
| WO1986002642A1 (en) | 1986-05-09 |
| AU573930B2 (en) | 1988-06-23 |
| EP0199794A4 (en) | 1987-09-28 |
| AU1333988A (en) | 1988-06-23 |
| CN85108193A (en) | 1986-12-17 |
| HUT41611A (en) | 1987-05-28 |
| KR870700612A (en) | 1987-12-30 |
| RO96607A (en) | 1989-03-30 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKLA | Lapsed | ||
| MKLA | Lapsed |
Effective date: 19930914 |