Note: Descriptions are shown in the official language in which they were submitted.
~-93/16079 ~ ) 2 7 8 Pcr/Ep~3/ool7l
':
. .
.:
.
.
;
.
Trlazolopyr~mtdlnesulfonamldes as herb1c~des
: .
'rhe present invention relates to novel herbicidally ac~ve and plant-growth-inhibiting
triazolo[l,5-a]pyIimidis~e-2-sulfonamides, to processes for theirprepara~on, composi~ons . .
. . containing these t~iazolopyrimidinesulfonamides as active ingredicnts, and to their use ~or
con~olling weeds, especially selec~vely in crops of useful plants, and for inhibiting the
: . growth of plants.
~,
1,2,~Tnazolo[1,5-a]py~imidine-2-sulfonamides which have a herbicidal ac~vity are.~ . known. Such compounds are desc~bed, for example, in US Paten~ 4 818 273.
. .
"~ Novel herbicidally acdve ~riazolo[1,5-aJpynmidine-2-sulfonamides have now been which
a}e dis~nguished from ~e 1,2,4-~iawlo[l,~-a]py~imidine-2-sulfonamid~s which havealready been disclosed by the fsct that they are more readily degradable~
'
. The S~iazolo[l,~-a]pylimidine-2-sulfonamides according to the invention are those of ~e ~
: formula I ~ .
''1 ' ' '
\Y ~ ~
~ R4
R~X R5
:~, . R
I R7 - `
-- . ~ .
in which Rl and R2 independently of one ano~her sre hydrogen, halogen, Cl-C4alln~
Cl-C4haloalkyl, C1-C4aL~coxy, C~-:C4haloaL~coxy, Cl-C4alkoxy-C~-C4-allyl, nitro, phenyl : .:
or S(O)nR3; R3 is C~-C4alkyl, Cl-C4haloalkyl, C2-~4alkenyl, C2-(:4alkynyl? benzyl or . ~ ~ .
; ~ . : optionally subs~n~ted phenyl; n;is ~e number 0, 1 or 2; R4, R5, R~,. R7 and R8
: ~D9rl6079 2105278 I'Cr/~93~00171
. -2-
independendy of one another are hydrogen or Cl-C4aL~yl; and ~ and Y independen~ly of
one another are hydrogen, Cl-C4alkyl or C3-C6cycloalkyl; .
and the agrochemically acceptable salts of these compounds,
- with the proviso that the radicals X and ~ aro no~ simultaneously hydrogen.
Halogen in the above definitions is to be understood as meaning fluorine, chlonne,
- . bromine or iodine, prefe~ably fluorine,.chlorine and bromine.
. . . . ' ' .
` ~ Suitable alkyl groups for Rl to R8, X and Y can be straighe-chain or branched alkyl
groups, for exa~nple methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl or
. tert-butyl; preferably alkyl groups having 1 to 2 carbon a~oms.
.. . .
. Haloalkyl groups which are suîtable for R1, R2 and R3 are alkyl groups which are mono-
.or polysilbstituted by halogen, halogen specifically being fluonne, chlorine, bromine.or
~ . ` iodine. Prefe~red ~rom amongst these.aLlcyl groups which are mono- or polysubstituted by
`. halogen are alkyl groups which are. mono- to tnsubstituted by halogen, in particular
', fluorine or chlorine, for example fluoromethyl, difluoromethyl, trifluoromethyl,
chloromethyl, dichloromethyl, trichloromethyl, 2,2,2-tlifluoroethyl, 2-fluoroethyl,
. - 2-chloroethyl and 2,2,2-trichloroethyl, preferably difluoromethyl and tnfluoromethyl.
Alkoxy radicals which are suitable for Rl and R2 are, for example, methoxy, ethoxy
propyloxy, iso-propyloxy, n-butyloxy, iso-butyloxy, sec-butyloxy and tert-butyloxy;
.l preferably methoxy and ethoxy. . .-
, 1 . . . . .
~.1 . . Haloallcoxy radicala which are suitable for Rl and R2 are, for example, difluoromethoxy,
., : .trifluoromethoxy, 2,2,2-trifluoroethoxy, 1,1,2,2-te.trafluoroethoxy, 2-fluoroethoxy,
2-chloroethoxy or 2,2-difluoroethoxy; preferably difluoromethoxy and trifluoromethoxy.
-~ . ,
Alkoxyalkyl radicals which are suitable for Rl and R2 are, for ~xample, methoxymethyl,
. methoxyeshyl, ethoxymethyl, ethoxycthyl alld propyloxymethyl. . . .
ln the case of R3, alkonyl is to be understood as meaning straight-chain or branched
i, . . . alkenyl, for example vinyl, allyl, methallyl, l-methylvinyl or but-2-en-1-yl; preferably . .
alkenyl radicals having a chain length of 2 to 3 carbon atoms.
In the case of R3 alkynyl is to be understood as straight-chain or branched aL~cynyl, for
.
~ .
,: : : .;, ~ ~ ~ - .
210 ~ 2 7 8 PCI`/EP93/û0171
... . 3 . .
example ethynyl, propargyl, l-methylpropargyl, but-2-yn-1-yl or but-3-yn-1-yl. . '
- . .Substituted or unsubsdtuted phenyl in the radical R3 iS a phenyl ring which is substieuted
- ' .. by 1 to 3 substituents, in particular halogen atoms, Cl-C3alkyl, Cl-C3haloalkyl,
' ' Cl-~3aLkoxy, C1-C3haloaL~coxy, Cl-C3alkanoyl, Cl-C3alkoxycarbonyl or eyano, or ma~ 'be .
' 1 to 2 nitro groups. ' .
` ' '',''' , '''
- ~ ' Exiamples of Ihe cycloaL~cyl radicals X and Y which are suitable as subs~tuents ase
` .. cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyi, preferably cyclopropyl.
' . The invention also embraces the salts of the compounds of the formula I, being
` . ' sulfonamides with an acidic proton, can fonn with arnines, alkiali metal bases and'alkalin~
; ` . . earth metal bases or quaternary ammonium bases. ` ' .' ~ .
. ' ' . ` . . Amongst allcali metal hyd~oxides and alkaline ear~ metal hydrbxides used in sialt
~' ` ' forsnation, the hydroxides of lithium, sodium, potassium, magnesium or calcium are
' prefened and particularly preferred are those of'sodium or potassium. ' .
. .:
Examples of arnines which are suitable for salt forrnation are plimary, secondary and. - '
'' '' . tertiary aliphatic and aromatic amines such as methylamine, ethylamine, n-propylamine, : ' `'"
isopropylamine, the four isomeric butylamines, n-amylamine, iso-asnylamine, hexylamine,
heptylamine, octylamine, nonylamine, decylamine, pentadecylamine, hexadecyLamine,
. ' ' ' heptadecylamine, octadecylarnine, methylethylamine, methylisopropylamine,
` '' methylehexylamine, methylnonylamine, methylpentadecylamine, rnethyloctadecylamine,.
: ethylbutylarnine, ethylheptylamine, ethyloc~lam~ne, hexylheptylamine, hexyloctyLarnine, ~.
`. ` ' dimethylamine, diethylamine, di-n-propylarnine, diisopropylamine, di-n-butylamine, ' ' ' ' ~
di-n-amylamine, diisoamylamine, dihexylamine, diheptylamine, dioctylamine, ~ '....... .
''7~ ethanolamine, n-propanolamine, iso-propanolamine, N,N~iethylethanolamine, ~ "
.j . N-ethylpropanolaminè, N-butylelhanolamine, allylamine, n-butenyl-2-amine,
` . n-pentenyl-2-amine, 2,3-dimethylbutenyl-~-amine, di-butenyl-2-amine,
.' ' n-hexenyl-~-amine, propylenediamine, diethanolamine, trimethylamine, triethylamine1 . ' .' :'
` ~ t~i-n-propylamine, ~iisopropylarni, tri-n-butylamine, hi-isobutylamine,
t ri-sec-butylarnine, ~ri-n-amylamine; heterocyclic amines for example pyridine, quinoline~
: '' iso~uinoline, morpholine, piperidine, pyrrolidine, indoline, quinuclidîne and azepine,
'~ . ' primary aTylamines, for example anilines, methoxyanilines, ethoxyanilines, ` .:
o,m,p-toluidines, phenylened;amines, benzldmos, naphthylamines and . ~
93/16079 ~ 1 0 ~ 2 ~ 8 P~CI/EP93/0017 ,,
-4-
o,m,p-chloroanilines; but in particular ethyl-, propyl-, diethyl- or ~iethylarnine, but
especially iso-propylamine and ,iiethanolamine.
: . ' . .
Examples of quaternary ammonium bases are generally the cations-of haloammonium
salts, for example the tetramethylammonium cation, the trime~hylbenzylammonium
cation, the ~iethylbenzyla nmonium cation, the tetraethylammonium cation, ~he
-- trimethylethylammonium cation, but also the ammonium cation.
.
Preferred are the compounds of the form,ula Ia
.~. x ,
Rl H N--N~
R ~ ~s~N NJ\y
, o~
.;,,, - ' o R6
R7
''.
i.e. Rl is in the 2-position, R2 the 3-, 4- or S-position, and the oxetan-3-oxycarbonyl
radical in the 6-position of the phenyl-l-amidosulfonyl ring. Particularly preferred,
amongst these compounds of the forrnula Ia a~e those ir~ which the radical R2 is in the 3-
or ~-posltion, and R4, Rs, R6, R7 and R8 independently of one another are hy~drogen or
-, ~ methyl,inpa~cularhydrogen.
-.,
.~.j . .
I ~ ; Other preferred compounds are those of the formula Ib
.1 ~ - X
~ `~S~ Y (Ib),
R6:
,1 . .
' i.e. Rl is in the 2-position, R2 in the 4-, 5- or 6-position and the oxetan~3-oxycarbonyl
radical is in thie 3-posi~on of tlle phenyl~ nidosulfonyl nng. Particularly profeIred
` :
93/16079 PCr/EP93/00171
` ` 2~0~278
. :
amongst these compounds of the formula Ib are those in which the radical R2 is in the
~position, and R4, Rs, R6, R7 and are R8 independently of one another are hydrogen or
methyl, in particular hydrogen.
: '
- Especially preferred are the compounds of ~he formula I, Ia or Ib in which the radical R2 is
hydrogen, fluorine, chlorine, bromine, methyl, methoxy or nitro.
.. .
Important compounds OI the formula I, Ia or Ib, including the preferred mean~ngs, are
those in which the radicalg Rl and R2 independently of one another are hydrogen, fluorine,
chlorine, bromine, Cl-C4aL~yl, Cl-C2haloalkyl or nitro. ~ardcularly preferred amongst
these compounds of the fonnula I, Ia or Ib are those in which Rl and R2 independently of
one another aro fluorine, chlorine, bromine, methyl, ethyl, trifluoromethyl or nitro.
. . . :.
.. .
~specially important compounds of the formula I, Ia or Ib, including all of the preferred
meanings, ar~ those in which the radicals X are hydrogen, methyl or cyclopropyl; and the
- radicals Y are methyl or cyclopropyl.
::;. . . . .
Compounds of the formula I, Ia or Ib which must be emphasised are the following, in
which Rl is hydrogen, fluorine, chlorine, bromine, methyl, ethyl or trifluoromethyl; R~ is :
- hydrogen, fluorine, chlorine, methyl or methoxy; R4, Rs, R6, R7 and Rg independently of
., one another are hydrogen or methyl; and X and Y independently of one another are `
hydrogen, methyl or cyclop~opyl.
~ :.
The process according to tl e invention for the preparaiion of the compounds of the
~ fo2~nula I ar~d salts thereof is analogous to known processes and comprises reactin~ an
i oxetan-3-oxycarbonylaniline of the formula II
. : ,
` NH2
' . . R~
R2 C-- R4 R5 (II)
` . ol ~ ~6
3 R7 ....
in which R1, R~, R4, Rs, R6, R7 and R8 are as dçfined in foImula I with a
' 1,2,~triazolo[1,5-a]pyrimidine-2-sulfonyl chloride of the forrnula I~I
1' ' '
~93/16079 ~ 2 7 8PC~/EP93/00171.
-6-
.~ X
N--N~ -
J~N 1N J\
SOicl y
in which X and Y are as defined in forrnula I, in an inert organic solvent in the presence of
a base. This process is pa~icularly suitable for oxetan-3-oxycarbonylanilines which have
ac~va~ng substituents, i.e. substituents which are electron donors, for example alkyl and
aLkoxy groups.
.
: Another process in ehree steps for the preparation of the compounds of the forrnula I
follows the equation:
- x x
. I N--N~ H N--N~
~ ~ S ~N . N y . Rl N ~N'lN'~
R2~ 0 ~ ~0 DR2~ 0 \o
COORg COOH :::
.. . .
VI~ IV
, . .
`. ~ ,
S\o ~Y ~7
ij . D R2 // ~o,N ~ D
? . O ~ .~ ~
` ! :
V .
! . An aLtcoxycarbonylphenyl-1,2,4-triazolo[l,S-a3pyrimidine-2-sulfonamide of the formula ~ `
VIII in which Rl, Ri, X:and Y are :as defined in formula I and E~ is Cl-C4alkyl is
J~ ~ : hydrolysed wi~h base catalysis to give the
hydroxycarbonylphenyl-1,2,4-triazolo[1,5-a3pyrimidine-2-sulfonamide of the formula IV
in which Rl, R2, X and Y are as defined above. . .
In a secondYeac~on step, this intennediate of ~the formllla IV is converted in the p~esence
s ~ ` - ;
~3 93/16079 210 ~ 2 7 8 PC~/EPg3/0017~
. .:
:: .
of l-hydroxybenzo~iazole and the acidic carbodiimide reagent
N-ethyl-N'-(3-dimethylaminopropyl)-carbodiimide hydrochloride into the activated ester
phenyl-(benzotriazol- 1 -yl-oxycarbonyl)- 1 ,2,4-triazolo[ 1 ,5-a]pyrimidine-2-sulfonamide of
the formula V in which Rl, R2, X and Y are as defined above. In a third reaction step, this
- ester of the ~orrnula V is reacted with 3-oxetanol of the forrnula IX in which R4, R5, R6, R7
and R8 are as de~lned in fonnula I, in a polar organic solvent at increased ~emperature tO
give the compounds of the formula I.
~; This second process for the preparation of the compounds of the formula I is preferred in
~hose cases where the oxetan-3-oxycarbonylanilines of the forrnula II are no~ accessible or
- cannot be reacted, or only with difficulty, with ahe
1,2,4 tnazolo[l,5-a]pyrimidine-2-sulfonyl chlorides of the forrnula III according tO the
first one-step process due to electron-attracting substituents Rl, R2, for example nitro,
S(0)2R3 or halogen. Such ~eac~ions of carboxylic acids which have an additional acidic
group (the sulfonarnide group in the abovementioned case) with the acidic carbodiimide
reagent N-ethyl-N'-(3-dimethylaminopropyl)-carbodiimide hydrochloride, are described
in J. Org. Chem. 47, 1962 (1982) and M. Bodansky & A. Bodansky, "The Practice ofPeptide Synthesis", p. 145, Springer Verlag 1984, in Volume 21 in the series "Reactivity
v and Structure, Conccpts in Organic Chemislry".
The reactions which give compounds of thc forrnula I are advantageously carried out in
aprotic, inert, organic solvents. Such solvents are hydrocarbons such as benzene, toluene,
xylene, hexane or cyclohexane, chlorinated hydrocarbons such as dichloromethane,j~ trichloromethane, tet~achloromethane or chlorobenzene, ethers such as diethyl ether,
ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran or
~dioxane, nitriles such as acetonitrile or propionitrile, amides such as dimethylformamide,
diethylformarnide or N-methylpyrrolidone, and esters such as ethyl acetate. The reaction
temperatures are preferably between -10C and ~150C`.
The reactions are generally not, or only weakly, exotherrnal and can be carried oot
belween 0C and room temperature. To shorten the reaction time or else to trigger the
reaction, it is expedient to heat the reaction mixture briefly at boiling point. The reaction
~' times can also 'oe shortened by adding either catalytic amounts or up to 2 equivalents of a
base as reaction catalyst. Bases which are suitable are, in particular, tertiary amines such
as trimethylamine, triethylamine, quinuclidine, 1,4-diazablcyclo-(2j2,2~octane,
-- - 1,5-diazabicyclot4,3,0)non-5-ene or 1,5-diazabicyclo(5,4,0)undec-7-ene or pyridine and
4-(N,N-dimethylamino)-pyridine. Altematively, inorganic bases such as hyd~ides, for
' '
- ~ ,
, .
~16079' 21~) 5 2 7 8 PCliEP93/00171
- 8 -
e~ample sodium hydside or calcium hy~ride, hydroxides, for example sodium hydroxide
and potassium hydroxide, carbonates, for exarnple sodium carbonate and potassium r
carbonate, or hydrogen carbonates, for exarnple potassil~m hydrogen carbonate and
sodium hydrogen carbonate, can also be used as bases~
Heterogeneous catalysis with transition metals, for example palladium, platinum or nickel
(Raney nickel) in absolute, inest, organic solvents, for example tetrahydrofuran or
dioxane, is preferably suitable for catalytic hydrogenation.
The end products of the forrnula I ~an be isolated'by concentration and/or by evaporation
of the solvent and purified by rec2ystallisation or trituration of the solid residue in solvents
in which they are not readily soluble, for exarnple ethers, esters, aromatic hydrocarbons or
chlorinated hydrocarbons. A further possibility for ;soiating and purifying the products of
the fosmula I is by means of ~flash) silica gel chromatography with the aid'of a suitable
solvent or solvent mixture, for example ethyl acetate, hexane or tetrahydrofuran.
The intermediates of the forrnula II are novel and were developed specifically for
synthesisin`g the compounds of the forrnula I. They are therefore part of the present
invention.
., .
- The novel intermediates oxetan-3-oxycarbonylanilines o~ the formula II can be prepared ~- -
by a range of st~ndasd processes known from 'the literature, for example by the following
equadon: ' '
.
.,
';l , . ~
. . - , :
.
., - .
~'. ' ' , ;
,
'~
~, ....
:
' ' ' ' '. . '
~ 93/16079 21 a a 2 7 ~ PCI~/EP93/00~71.
'.! . . .
,'` . ' .
- - 9 ~
- . .
, . ~R6
Rl 2 SC~2 or Rl NO~L R8 R7 R ~ R4 RS R
Cl(CO)2Cl ~ N(C2H5)3 C ~~
.. R2 COOH R2 COCI O ,~
R8 R7
.: . V~ Vl ' `
¦ o~N~ / N U2/c~
R1 N2 NH2
0/ ~ D ~--8
IR7 R O
~ VI R7
,. ,, : II
.
. Accordin~ly, the compounds of the forrnula II are obtained by reacting a ni~robenzoic acid
derivadve of the formula VII in which Rl and R2 are as defined in formula I with''!~, . . " ' N,N-bis(2-oxo-3-oxazolidinyl)phosphinic aGid chlonde ~see Synthesis 1_, 547~, or
- thionyl chloAde, oxalyl chloride and 3~xetanol of the fonnula lX~in which E~4, Rs, 1~6.1~7
:~ ~ . . and R8 ~re as defirled in formula I, in the presence of a suitable base, for example
ie~hylamine, to give a compound of the fonnula VI in which Rl, R2, R4, R5, R6, R7 and
R8 are as defirled in fonnula I, and subsequently subjecting this intennediate to catalytic
~, i hydrogenation in an inert solvent.
.,i' , - ' . ' .
The intermediates oxetan-3-oxycarbonylnitrobenzenes of the fonnula YI are also noveI
.1 , and accordingly a further part of the present inven~on.
.,j . ~.
Th~ same preferred meanings wi~h respect to RI, R2, R~, R5, R6, R7 and E~8 as in the
compounds of the fonnula I apply to the h~lo interrnediates of the formulae 1~ and ~'I. : . ;
.. 1 . : ' . .:
. - . ; Tile star~ng compounds required for the preparation processes are either hlown o~ can b~ .
prepared readily from known compounds. ~ ~ :
`'4
.
:~ 93/16079 21 0 ~ 2 7 8 PCI/EP93/00171
. .
- 10- .
'
:
The 3-oxetanols of the fonnula IX
R5
R4 \~R6
HO~CO (~X),
R8 R7
in which R4, Rs, R6, R7 and R8 independently of one another ar~ hydrogen or methyl are
known from the literature; see J. Org. Chem 48, ~953 (1983); ~. Am. Chem. Soc. 112,
3535 (1990); Tetrahediron Lett. 30j 2505 (1969); Bull. Chern. Soc. Japan 62, 2032 (1989);
and J. Am. Chem. Soc. 77,`4430 (1955).
., - , .
~ . . . . .
`~ 'rhe 1,2,4-triazol~[1,5-a]pylimidinesulfonyl chlorides of the foImula III
., ~ . .
.. ' I , j ,.
N--N~
: ~N'lN'~\ .
.~ . .
are described in US-A-4 818 273 and EP-A-387 508.
~.
;j The carboxylic acid derivatives o~ the formula VIII
x . . ..
R~ O~` ~O r VIII),
COOR9 :
~, .
i ~ in which Rg is hydrogen or Cl-C4alkyl are disclosed in US-A-4 818 273 and
EP-A-434 624.
As a rule, the active ingredients of the fonnula I are successfully applied at application
ates from 0.001 to ~ kg/~a, in~particular 0.005 to 1 kglha. The dosage rate required for the
desired effect can be dete~ined by expenmen~s. It depends on the type of action, the - ~ -
- development slage of ~he crop plan~ and of the woed and on the application (location, timç,
method) and can vary within wide ranges due to these parameters.
The compounds of the formula I àre distinguished by grow~h^inhibitlng and herbicidal
pro{ enies wl~ich make them outstandingly sllitable for use in crops of use~ul plants, in
1~ 93/16079 21 ~ a ~ 7 8 PCr/EP93/00171
- 11 - ,
particular in cereals, cotton, soya beans, oilseed rape, maize and rice, the use in coKon,
soya crops and cereals being very particularly preferred. ~Teeds in cotton and soya crops
are preferably controlled pre- and post-emergence. The compounds of the ~onnula I are
d stinguished in particular by the fact that they are readily degraded.
The invention also relates lO herbicidal composidons which comprise a novel active
ingredient of the formuIa I and to a method for inhibiting the growth of plant~9.
.,
A method for inhibiting plant growth is understood as meaning controlling the natural
development of the plant without altering the life cycle of the plant, which is detennined
by it~s ~enetic make-up, in the sense of a mutation. The method of growth inhibition is
` applied at a particular point in time of the development of the plant, which is to be
.' ` det~mined in the par~cular case. The active ingredients o~ the formula I can be applied
` before or after emergence of the plants, for example even to the seeds or seedlings, to
roots7 tubers, stalks, leaves, flowers or other parts of the plants. This can be effected, for
- example, by applying the active ingredient, as pure active ingredient or in the fonn of a
composition, to the plants and/or by treating the nutriçnt substrate of the plant (soil).
`, . . , :
` Various methods and techniques are suitable for using the compounds of the formula I or
compositions comprising them for inhibiting plant growth, for example the following:
. . . . .
'Z i) Seed trea~nent
a) l~e seeds a~e treated with an active ingreclient formulated as a wettable powder by .
``~;Z sh~ldng in a conta~ner undl the seed surface is uniformly covered (dry seed treatment)~ Up
Z to 4 g of active ing~dient of the fonnula I are used per kg of seed in ehis method (up to
' . 8.0 g of wettable powder in dle case of a 50 % formulation).
~, .
b) The seeds are treated with an emulsion concentrate of the active ingredient or with an
aqueous solution of the active ingredient of the formula I formulated as a wettable powder,
using method a) (wet seed s~eatment).
. c) Seed treatment by immersing the seeds in a liquo~ containing up to 1000 ppm of acdve ;
ingredient of the fonnula I for 1 ~o 72 hours, which, if desired, is followed by dlying the
] seeds (se~d soaking).
Naturally, seed ~eatment~ or ~eatment of the genninated seedling are the preferred
,~ - ' . :
' ' ' ':
~93/1~07~ 2 1 0 ~ 2 7 8 PCr/EPg3/00l7l
.
.
- 12-
applicalion me~hocis since the treatment with ae~ive ingredien~ is direc~ed entirely at the
target crop. As a rule, 0.001 g to 4.0 g of ac~ive ingredient are used per kg of seed, but it is
possible to deviate from the limit concentrations given in both direc~ions, depending on
ihe method chosen which also makes possible the addition of other active ingredients or
micronuments (repeated seed treatrnent).
ii) Controlled release of active in~redient
The dissolYed ac~ive ingredient is applied to rnineral granule carriers or polymerized
granules (urea/forrnaldehyde) and allowed to dry. If desired, a coating can be applied
(coated granùles), which permits controlled release of the actiYe ingredi~nt over a certa~n
period.
, , ' '', ..
The compounds of the forrnula I are employed in unaltered forrn, as obtained from
synthesis or preferably together with the auxiliaries conventionally used in the art of
formulation, and they are therefore processed in a known manner to give, for example,
emulsion concentrates, directly sprayable or dilutable solutions, dilute emulsions, wettable
powders, soluble powders, dusts, granulés, and also encapsulations, for example in
polymeric substances. The application methods, s-~ch as spraying, atomizing, dusting,
wetting, scattering or pouring, as well as the kind of the compositions are selected to suit
the intended aims and the prevailing circumstances.
. . ,
The forrnulations, i.e. the compositions, preparations or combinations comprising the
active ingredient of the f.onnula I and, if desired, one or more solid.or liquid additives, are ~ -
prepared in a known-manner, for example by intimately mixing andfor grinding the active
ingredients with extenders, for example with solvents, solid carriers and, if desired,
surface-active compouslds (surfactants).
;i , , - . ~ . .
;, .
The following are possibl~ as solvents: aromatic hydrocarbons, in particular the fractions
C8 to C12~ such as mixtures of alkylbenzenes, for example xylene mixtures or alkylated
naphthalenes; aliphatic and cycloaliphatic hydrocarbons such as paraffins, cyclohexane. or
tetrahydrQnaphthalene; alcohols such as ethanol, propanol or butanol; glycols as well as
their ethers and esters, such as propylene glycol or dipropylene glycol ethers, ketones such
as cyclohexan;one, isophorone or diacetone alcohol, strongly polar solvents such as
N-methyl-2-pyrrolidone, dimethyl sulfoxide or w~ater; vegetable oils as well as esters
thereof, such as rapeseed, castor or soya oil; or, if desired, silicone oils.
.
-
', : '.'
~ 93/26079 21~ ~ 2 7 8 PCI~/~P93/00171
,
, . . .
- 13-
'': . ...
Solid caniers which are generally used, for example for dusts and dispersible powders, are
ground natural minerals, such as calcite, talc, kaolin, mon~norillonite or attapulgite. To
improve the physical properties, it is also possible to add highly~isperse silicas or
highly-disperse absorpdve polysners. Possible particulate, adsorptive carriers for granules
ar .either porous types, for example pumice, brick ~t, sepiolite or bentonite, or
nosl-soIptive ca~ier mateIials, such as calci~e or sand. Moreover, a lar~e number of
pregranulated materials of inor~anic or organic nature can be used, such as, in particular,
dolomite or comminuted plant sesidues.
Suitable surface-active compounds are non-ionic, cadonic and/or anionic surfactants
having ~ood emulsifying, dispersing and wethng properties, depending on the nature o~
the active ingredient of the forsnula I to be fonnulated. Surfactan~s are also to be
und~rstood as meaning mixtures of surfactants.
.
Anionic surfaetants which are suitable can be either so~alled wa;~.-soluble soaps or
water-soluble synthetic surface-active compounds.
Suitable soaps which may be mentioned are the alkali metal salts, alkaline earth metal
salts or substituted or unsubstituted ammonium salts of higher fatty acids (ClO-C22~, such
as the sodium salts or potassium salts of oleic or stealic acid, or of natural mixtures of
fatty acids which can be obt~ined, for example, from coconut or tallow oil. Mention m~st
also be made of ~he faKy acid methyltaurinates.
.. . .. .
However, s~called synthetic susfact~nts are used more frequently, in particular fat~y
,- alcohol sulfonates, fatty alcohol sulfates, sulfonated benzimidazole derivatives or :
alkylarylsulfonates .
The fatty alcohol sulfonates or fatty alcohol sulfates are as a rule in the fonn of alkali
mesal salts, aLlcaline earth metal salts or substituted or unsubstituted ammonium sa1ts, and
have an allcyl radical having 8-2X C atoms, allcyl also including the aLtcyl moiety of acyl
- radicals, for example the sodium or calcium salt of ligninsulfonic acid, of the
dodecylsulfuric ester or of a fatty alcohol sulfate mixture prepared from natural fatty
acids. This group also includes the salts of the sulfuric esters and sulfonic acids of fatty
alcohoVethylene oxide adducts. The sulfonated benzimidawle de~iva~ves preferablycontain 2 sulfonyl groups and one fat~ acid radical having 8 to 22 C atoms. ~xarnples of
aLlcylarylsulfonates are the sodium/calcium or ~iethanolamine salts of
- : :
. ' " . ' ' ' .
~ 1:0 ~ 2 7 8 : . PCI`/EP93/OU171
'' ' - ' ' ' ~' ' ''
- - 14 -
dodecylbenzenesulfonic acid, of dibutylnaphthalenesulfonic acid or of a
naphthalenesulfonic acid/formaldehyde condensation product.
Other suitable compounds are the cor~sponding phosphates, snch as the salts of the
phosphoric ester of a p-nonylphenoV(4-14)-ethylene oxide adduct, or phospholipids.
~ . - ' . '. .. .
Suitable non-ionic surfactants are mainly polyglycol ether derivatives of aliphatic or
cycloaliphadc alcohols,'saturated or unsaturated ~atty acids and alkylpilenols, which can
~'' contain 3 to 30 glycol ether groups and 8 to 20 carbon atoms in'the (aliphatic)
" hydrocarbon radical and 6 to 18 carbon atoms in the alkyl radical of the alkylphenols.
;.,~ -
-^. ' Other non-ionic surfactants which are suitable are the wate~-soluble polyethylene oxide
adducts with polypropylene glycol, ethylenediaminopolypropylene glycol and
aLkylpolypropylene glycol which have 1 to 10 carbon atoms in the aLcyl chain and which
` ' contain 20 to 250 ethylene glycol ether groups and 10 to 100 prowlene glycol ether ' .
groups. The abovementioned compounds customarily contain 1 to 5 ethylene glycol units
per propylene glycol unit.
i. . . .
.^, Examples of non-ionic surfactants which may be mentioned are nonylphenol
J ' ' polyethoxyethanols, castor oil polyglycol ethers, polypropylene/polyethylene oxide . ~
. adducts,' tributylphenoxypolyethoxyethanol, polyethylene glycol and ' '
octylphenoxypolyothoxyethanol.
ther suitable substances are fatty acid esters of polyoxyethylene sorbitan, such as
. ~ polyoxyethylenesorWtan trioleate. -
~, . .
. ~ . . . .
~"~ ' The cadonic surfactants are mainly quaternary ammonium salts, which contain at least one
' aLIcyl radical having 8 to 22 C atoms as N-substituents and which have lower, possibly
' halogenated alkyl, benzyl or lower hydroxyalkyl radicals as further substituents. The salts
are preferably in the forrn of halides, methylsulfates or ethylsulfates, for example~ '- '
stearyl~imethylammonium chlofide or benzyldi~2-chloroethyl)ethylammonium bromide.
'il The surfactants cus~omary in thc art of forrnulation are described, inter alia, in the ' '
foilowing publicadons: ' .
-~ ~ " "Mc Cutcheori's De~ergents and Emulsiifiers Annual" Mc Publishing Corp., Glen Rock,
New Jersey, 1988;
i : ~ - .: .
~) 93/16079 2 ~ ~ ~ 2 7 8 Pcr/EPg3/ool7ll
?~
. .' . '
- 15- , .: '
. . .
- M. and J. Ash, "Encyclopedia of Surfactants", Vol. I-III, Chemical Publishing Co., New
York, 1980-1981.
- : Dr. Helmut Stache, "Tensid-Taschenbuch rSurfactant Guide]", Carl ~anser Verlag,
Munich, Vienna, 1981.
.
~ As a rule, the pesticidal preparatiolls comprise 0.1 to 99 %, in particular 0.1 to 95 %, o~
. . the acdve ingredient of the fo~ula I, 1 to 99 % of a solid or liquid additive and O to 25 %,
in par~cular 0.1 tD 25 %, of a surfactant.
.; ... ' , .
- While concentrated compositions are more prefeIred as commercial products, the end
user, as a rule, applies dilute compositions.
: .
The compositions can also comprise further additives such as stabilisers, for example
- . e?poxidised or unepoxidised vegetable oils (epoxidised coconut oil, rapeseed oil or soya
oil~, defoamers, for example silicone oil, preservatives, viscosity regulators, binders,
. tackifiers as well as fertilisers or other active ingredients for achieving specific effects.
. ~. ,. . . : ..
In particular, preferred formulations have the following composition: (% - percent by .`
weight).
:~ .
. ,:.
.~ - ' Emulsifiable concentrates~
Active ingredient: 1 to 90 %, preferably 5 to 50 %
Sur~actant: S to 30 %, preferably lO to 20 % ~ `
.; ` Liquid ca~rier: 15 to 94 %, preferably 70 to 85 %
? Dusts:
Active ingredient: 0.1 to 10 %, preferably 0.1 to 1 %
Solid carrier: 99.9 to 90 %, preferably 99.9 to 99 %
' .
' ..... .... .. ........... . Suspension concenttates:
Acti.ve ingredient: S to 75 %, preferably 10 to 50 %
Water: 94 to 24 %, preferably 88 to 30 %
? Surfactant: 1 to 40 %, pleferably 2 to 30 %
? ' j :
.. . . ..
-
.. ''' ' ' ' : : . . '~
` ' '
~ 93/16079 21 O ~ 2 7 8 pcr/Ep93/ool71
.
.
Wettable powders: .
Active in~redient: 0.5 to 90 %, preferably 1 to 80 %
. - Surfactant: 0.5 to20%,preferably 1 to 15 %
Solid caIrier material: S to 95 %, preferably 15 to 90 %.
. , . :
Granules:
Active ingredien~: 0.~ ~o 30 %, preferably 3 to 15 %
Solid carrier: 99.5 to 70 %, p~eferably 97 to 85 %.
- ' ' ' '
: ~ Forrnulation examples of liquid active in~edients of the formula I
" (% = percent bY wei~ht)
, :; - . ,.
~ , .
~- 1. Emulsionconcentrates a) b~ c)
:; - , .
.` Active ingredient as per
Tables l.and2 2S% 40% 50%
Calciumdodecylbenzenesulfonate 5% 8~o 6%
.- . Castor oil polyethylene glycol . - :
. ether (36 mol of EO) 5% - - -
Tri~utylphenol polyethylene
`. glycol ether (30 mol of EO) - 12% 4%
. Cyclohexanone - 15% 20%
ylenG mixture 65% 25% 20%
q ~ Emulsiot~s of any desired concentration can be prepared from such concentrates by
diluting them with water.
:. : . - . '
.,' . . . . .
,., ' '
' ' '
.y
l .
.. s . . . . . , . - .. ,
,~ ~ -. .
.~ , .
.' , . .
~: . . : . .
~ 93/16079 2 1 ~ ~ 2 7 8 PCr/EP93J00171
.
! . ., ' . .
17
.
. Solutions a) b) c) d)
- Active ingedient as pcr
. Tables 1 and2 80% 10% 5% 95
Propylene glycol monomethyl
- . ` ether 20%
: ~ . Polyethylene glycol MW 400 - 70% - -
- N-Methyl-2-pytrolidone - 20% ~ -
` Epoxid~sed ~oconut oil - - 1% 5%
Petroleum Spilit (boiling
` range l~lgOC) - - 94%
~ .
:. . The solutions arei suitable for use in the fo~m of microdrops.
- ~ . ... .
` ~ . 3. Granules a) b) c) d~ .:
; Active ingredient as per . : :
. ; Tables 1 and2 5% 10% 8% 21%
- : Kaolin 94% 79% ~4%
Highly-disperse silicic acid 1% - 13% 7%
., Attapulgite - 90% - 18% :
The active ingredient is dissolved in methylene chloride, the soludon is spraycd onto the
. caxIier, the solvent is subsequently evaporated in vacuo.
4. Dus~s a) b) .
...... Active ingredient as per
. . Tables 1 and 2 2% 5%
~:~i Highly-disperse siiicic acid 1% 5%
.~ Talc 97% . : .
~ ' Kaolin - 90% . - `
.$ i . . .
;~ ... . .
:~ . . Ready-for-use dusts are obtained by intimately mixing the ca~Tiers with tne ac~ive
ingredient,
.~ , . .
~,.~ - . .
.. .
: . . - .
,,
.'
~i ' ', ,.. .
- . . ~ , ~ . . . . . . .
/16(179 2 i O 5 PCI/EP93/00171
Fonnulation examples of solid active in~redients of the forrnula I
(% = percent bY wei~ht)
. ' ' . .
5. Wettable powders a). b) c)
Active ing~edient as per '
Tables 1 and2 25% ,50% 75%
S'odium ligninsulfonate ' , 5% 5%
Sodium lauryl sulfate' 3% - ~%
Sodium diisobutylnaphthalene- .,
sulfonate - 6% 10%
Octylphenol .polyethylene
glycol ether (7-8 mol of EO) - 2%
Highly-disperse silicic acid 5% ~ 10% 10%
Kaolin 62% 27%
. . . . .
` The active ingredient is mixed thoroughly with the additives, and the mixture is ground ' '
. ~ ' thoroughly in a suitable mill. This gives wettable powders which can be diluted with water
`. . to give suspensions of any desired concen~tion.
:i 6. Emulsion concentrate
ctive ingredient as per
,`~ Tables 1 and 2 ' 10%
.'; . Octylphenol polyethylone glycol . .-
r~ . . ether ~4-5 mol of EO) 3% ' : '
',' Calcium dodecylbenzenesulfonate ' 3%
'', . Castor oil polyglycol ether
'~ (36 mol of EO) , 4%
'. Cyclohexanone . 30% . ~
., Xylene mixture 50% ' ' ' " .',
, . . .
l . . Emulsions of any desired concentration can be prepared from this concen~ate by diluting. : :~
! itwith'water. : ' .
I; ' ' ' ' . ' . .
~, . ' ' .
. . . . .
.;: , .
,
i,,., ,. ... . . .. . ; ., . . . :.. . .. . . ... .
;
~3/T6079 2 1 0 5 2 7 8 PCT/EP93/00171 :
" : . . . .
-. . - 19~ .
- 7. Dusts a) b)
- Active ing~edlent as per
- - Tables 1 and 2 ~% 8%
Talc 95%
Kaolin ~ 92%
','': '., .: ' :
Ready-for-use dus~s are obtained by mixing the acdve ingredient with the came~s and
gnnding the mixture on ai suitable mill.
, . - .
8. Extmder granules
Acdve ingredient as per
- Tables 1 and 2 10%
Sodium ligninsulfonate 2%
` Ca~boxymethylcellulose 1%^ Kaolin ~7%
,, ':
The active ingredient is mixed with the additives, and the mLl~ture is gmund and moistened
-' with water. 1 his mixture is extruded and subsequently dIied in a stream of air.
..,~............ . . ..
,: 9. Coated ~ranules
- Ac~ive ingredient a~i per
,~ Tables l aIId 2 3%
Polyethylene glycol (MW 200) 3%
i;~, Kaolin 94%
.. . . . ..
In a mixer, the finely ground active ingredient is applied uniforrnly to the kaolin which has
been moistened with polyethylene glycol. Dust-free coated granules are obtained in this
manner.
" . ' '' ' '.'
,~ 10. Suspension concentraite
;, Acdve in~ent as per
Tables 1 a~d 2 40%
opylene glycol 10% ~-
; ~ Nonylphenol polyethylene glycol
!, ether (15 mol of EO) 6%
Sodium ligninsulfonato ~ 10% ~ -
;, , . ' :
~ 93~16079 PCr/EP93/~0171
2~27~
~ . ' , .
- 20 -
Carboxymethylcellulose1%
Silicone oil in the form of a
75% aqueous emulsion 1%
Water 32
.'.... , , . . '' '
The finely ground acdve ingredient is mixed intimately wii,h the additives. ~ suspensio
concentrate from which suspensions of any desired concentration can be prepared by
dilution with water is obtained in this manner.
PreParation Examples
`~ Example Hl: PreParation of 5,7-dimechvl-N-~2-meth~1-6-(3-oxetanyl)-
oxvcarbonylphenvll- I !2~-triazolo~ 1 .5-al-~rimidine-2-sulfonamide
r
CH
pz~ , , .
N _ N ~ CH3 .
~NH;OL (~ 04
. . ,:
, O , : ~:
.1, . . , ' , . '
`~1 3.1 g of 3-oxetanyl 3-methylanthranilate (cf. Preparation Examples H5 and H6) and 3.7 g
' of 5,7-dimethyl- 1 ,2,4-triazolo-[ 1,5-a~-pyIimidine-2-sulfonyl chloride are stirred for 20
- hours at room temperature in S ml of pyridine and 5 ml of ethyl aceta~ . The reaction
mixture is poured into ice-~ater and extracted twice using ethyl acetate. The organic
phase is washed in each case once with water, 2N hydrochloric acid, water and satùrated
sodium chlonde solution, dried over sodium sulfate and concentrated. The cnude product
- is subjected tO flash chrom~tography over a silica gel column using ethyl acetate/hexane
9/1. The desired product 5,7-dimethyl-N-[2-methyl-6-(3-oxetanyl)-oxycarbonyl-
phenyl]-1,2,4-triazolo[1,5-a]py~imidine-2-sulfonamide has a melting poirit of 174-175C. ~ ~
,:
:, .-i: . . .
. .
~ 93/16079 21 a ~ 2 7 8 PCI/EP93/00171
,: . ,.
-21 -
:' ' '
Example H2:
~-MethYl-7-c-~clopropYl-N-(2-chloro-~hYdroxycarbonvlphenYI)-1,2,4-~iazol~
rl ~S-alpyIimidine-2-sulfonamide
t~te~nediate) , ...
:.
.,-,
~ .
N ,N~ CH3
Cl J--N
: ' 1 NHS02/
:` `' ~ ' `
., COOH
,
; 4.1 g of 5-methyl-7-cyclopr~pyl-N-(2-chloro-~methoxycarbonylphenyl)-l,2,~1ria~olo- `
~l,S-a]pyrimidine-2-sulfonarnide are s~ed for 2.5 hours at 6~6~C in 100 ml of 2N
sodium hydroxide soludon. The mixture is brought to a pH of 2.8 with the aid of
~ . half-concentrated hydrochloric acid which is added dropwise while the mix~ure is cooled . :. .
" ` to 0-5C. The product which has precipitated is filtered off, washed with buffer solution` : :
` (pH 3) and dried over phosphorus pentoxide in a vacuum desiccator at 70C. 3.48 g of ~e
- dèsiredS-methyl-7-cyclopropyl-N-(2-chloro ~hydroxycarbonylphenyl)-1,2,~i,awlo-E~,5-a]pyIimidine-2 sulfonamide of melting point >~15~C (decomposition) are obtained.
' ' ` `:
., .. ' ' . '
... . .. .
_ , .. . .
: .
. .
. . . . . .. ~ . , .. .
'.. :", ' . ,', :,
~ . .
-. ' ~" .
:
~ 93/16079 210 .~ 2 7 8 Pcr/Eps3/oul7l
,
- 22 -
- ExamPle H3:
S-Methyl-7-cYclopropyl-N-r2-chloro-~(benzo~iazol- l-Yloxycarbonyi)-phenyll-
1 ~2~4-triazolor l ,5-alpYrimidine-2-sulfonamide
(Intennediate)
. : , .
~ '. .
Cl /I~N CH3
' ~ l NE IS2
,~ ~/ , . . . .
:- ~C/ \N~ ~N
O ~ ~
, 4.76 g of 5-methyl-7-cyclopropyl-N-(2-chloro-6-hydroxycarbonylphenyl)-1,2,4-triazolo-
~ [1,5-a]py~imidine-2-sulfonamide and 1.69 g of d~ l-hydroxybenzotriazole in lO0 ml of
i dichloromethane are treated, with ice-cooling, with 2.5 l g of ; ;
.~ N-ethyl-N'-(3-dimethylaminopropyl)-carbodiimide;hydrochloride, and the mixture is
sti~red for 1.5 hours. A clear, dark yellow solution results, and this is beated to room
.:! temperature and left to stand overnight. The reaction solution is washed in each case twice
d~ with buffer solution ~pH 5.12) and saline, dried and evaporated, and the product is
subjected to flash chromatography on 200 g of silica gel with tetrahydrofuran as eluent
and recrystallised from ethyl acetate. 3.1 g of the desired 5-rnethyl 7-cyclopropyl-
N-12-chloro-6-(benzotriazol- 1 -yloxycarbonyl)-phenyl]- 1 ,2,4-triazolo[ 1 ,S-a]pyrimidine-2-
i : sulfona~nide of melting point 180-185C are obtained.
. :
2 ~`93~16079 2 :~ O ~ 2 7 8 PCr/EP93/0017l
' . .
- ~3 -
, ~ .
Example H4:
~-Me~hYl-7-cyclopropxl-N-r2-chloro-~(3~x ~anvll-oxYcarbo~n~lphenyl~ 2,~triazol~
`~ rI,5-alpYrimidine-2-sulfonarnide
'.. '' .. ' ~
" ` N /~--CH3
~' ' ` - ` C ~ , "
\,,0
.~ , ` ' `' '~
.
1.9 g of ~-methyl-7-cyclopropyl-N-[2-chloro-~benzo~iazol-1-yloxycarbonyl~phenyl]- ` ~:
1,2,~iazolo[1,5-a]pyrimidine-2-sulfonarnide and 1.2 g of 3-oxetanol (content X0%) are
reflwced for 76 hours in 50 ml of acetonitrile. The reac~on mixture is evaporated, and t}~e
product is subjected to I1ash chromatoglaphy on 250 g o~ silica gel using ethyl acetate/
tetrahydrofuran 18/4. The product is recrystallised from ethyl acetate and ~ied for 3 hours
under a high vacuum at 100 11ûC (removal of crystal solvent~. 0.79 g of ~he des3red
5-methyl~7-cyclopropyl-N-12-chloro ~(3-oxetanyl)-oxycarbonylphenyl]-1,2
iazolo[1,5-a~py~isnidine-2-sulfonamide of melting point 187-190C is obtained. :~
Example H5. 3-Oxetanyl 3-methyl-2-ni~obenzoate
~Intennediate)
~ . .
'': " .. CH3
~3( o (3 05)
1 o
,
. I7.0 g af 3-methyl-2-nitrobenzoic acid, 7.5 g of 3-oxetanol (content 92%) and 18.7 g of - :
~iethylamine a~e introduced:into ~200 snl of dichloromethane. 23.7 g of
N?N-bis[2~x~3~xazolidinyU-phosphinic acid chloride are added in one portion with `
:
: . ,:
~93~16079 2 1 0 ~ 2 7 ~ PCr/E:P~3/0017
- 24 -
vigorous sti~ring and cooling to 15C. The ice-bath is removed after lO minutes; the
reaction temperature rises slowly to ~30C. After 2, hours, a clear solution is obtained
which is left to stand ovemight. The reaction solution is washed twice using saturated
sodium bicarbonate so}ution as well as saline, dried over sodium sulfate, and the solvent is
evaporated. The residue obtained is dissolved in a mixture of diethyl ether/ethyl acetate.
This solution is treated with active charcoal while hot. The crude product is concentrated,
-- then recrystallised from ether, and washed with an ether/pentane mixture. 12.5 g of the
desired 3-oxetanyl 3-metbyl-2-ni~obenzoate OI melting point 78-80C are obtained.
.
ExarnDle H6: 3-Oxetanvl 3-methvlanthranilate
`- (Intermediate~
.
` H3C
~X / ~ (3.063
, , . ' ,, ',
-. .
12.0 g of 3-oxetanyi 3-methyl-2-nitrobenzoate in lS0 ml of tetrahydrofuran are
hydrogenated with 2.5 g of Raney nickei under ai~mospheric pressure, and 2 more portions
of catalyst of 2.5 g each are added in the course of the reaction. The catalyst is
i subsequently filtered off, and the tetrahydrofuran is evaporated. The crystalline residue is
' sti~red with ether and filtered off. After drying at 40C, 7.9 g of the desired 3-oxetanyl
3-rnethylanthranilate of melting point 90-92C are obtained.
i - - . :.
The compounds of the formulae Ia and Ib which are listed in the following Tables I, 2 and
.1 3, as well as the intennediates thereof, are prepared analogously.
:. . . .
.. . .
;~ . '.' . ~.
~! . , , ~ . :
. ' ~ ` ' ` ' . ,.
,,~ . , ., . . , . , - :
,! . . :
~ ,:
., ~ . ~ ~ . ,` . .,
! -
i . . `
; . ~93/1607~ 21~27~ P~T/~3/00171
:.
. .: ..
~ 25-
:. .
~ . Table 1: ~mpounds of ~e fonnula Ia
: ' I ' ''
: N- N~,
,~ N51N~1Y (Ia)
: R~ ~0>~ :
R4
:: -
. . Comp.
No. Rl R2 R4 Rs X Y M.p.
. .
. .
~` 1.01 H H H H ~ CH3 146-147C
`.i 1.02 CH3 H H H ~ CH3 118-12aC . .
.; 1.03 H H H H CH3 CH3 139-140C
~;i . 1.04 OEI3 H H H C~H3 CH3 174-175C
~l 1.05 H H H H H CH3 165-166C
.~ 1.06 CH3 H H H H CH3 168-170C . .
' ~ 1.07 Cl H H H ~ CH3 187-190C
~ ~. . 1.08 C2H5 H H H CH3 CH3 14~-150C .:
` . 1.09 F H H H C~H3 CH3 185-187C . .
-~ 1.10 F ~ H H H ~ CH3
; 1.11 F H H H H CH~ :
l . 1.12 Cl H H H H CH3 > 145C
,~ 1.13 Cl H H H ~ C~H3
;~ : . 1.14 : C2H5 H H H ~ CH3
1.15 C2Hs H:: H H H C~3 ~ 161-162C
1.i6 CH3 H H H~ CH3 ~
',1' ' ' . ' ~
~D9~16079 210~78 rcr~ /ool7l
- 26 -
:~ Comp.
No. Rl R2 R4 Rs X- Y M.p
- - ./1
-- 1.17 Cl H H H CH
. 1.18 F H H H. CH3 ~
1.19 C2H5 H ~ ;:
1.20 CH3 H . H H CH3 H 152-153(~
- 1.21 F H H H CE~3~ H ~.
1.22 Cl . H H H CH3 H . .~
1.23 C2Hs H H H CH3 H . . ::
- 1.24 Br H H H CH3 CH3 . .~
.- 1.25 Br H H H H CH3 .
1.26 CH3 S-CI H H CH3. CH3 ~:;
1.27 -F 3-OCH3 H H CH3 CH3
1.28; -.CF3 H H H CH3 CH3 . . .:
. 1.29 CH3 H CH3 H CH3 CH3 ....
i 1.30 F. H . CH3 H CH3 CH3
~i . .1.31 Cl H CH3 H CH3 CH3
~ 1.32 ~ F HCH3: H - ~ CH3
4; .1.33 . CH3 HCH3 H CH3 CH3
~; 1.34 CH3 HCH3 H ~ CH3 . . ..
' ~ 1.3~ . F . HCH3 H CH3 CH3 ..
q . . 1.36 F HCH3 H ~ CH3
~ ... .
1.37 F H . CH3 H H . CH3
1.38. ~ Cl . . H CH3 H CH3 C~3
; . 1;39. CI H~ CH3 H ~. CH3. . :
~: : . 1;40 Cl HCH3 H H CH3
- i.- . .
~ 93/16079 21~ ~ 2 7 8 Pe~EP93/0Q~71
- 27 -
:. ' :
- COmP.
NO. Rl R2 R4 R5 X Y MP
~; 1.41 ~ H H CH3 CH3 CH3
. 1.42 CH3 H H C~3 CH~ CH3
` 1.43 C3H7(i) ~ H ~I H CH3 19~197C
. ~ " . .
- Table 2: Compounds of the formula Ib
x . . .
N--N~, :
~NU~ N1N1CU3 (Ib)
O ' '
... . . .
COmP.
. . NO. R1 R2 X R4 R5 M.P.
. . . .
;.
2.01 Cl Cl CH3 H H
2.02 Cl Cl H
2.03 Cl ~ Cl ~ H: H
2.04 Br CH3 CH3 H H
2.05 Br CH3 H H H
2.06 Br C~H3 ~ H H
2.07 F F CH3 H H
2.08 F F ~ H H
2.09 ~ CH3 F ~ CH3 ~ ~ H H
2.10 CH3 C~l CH3 H H
2.11 CH3 F --<3 H H
2.12 ~ ~ CH3 F ~ 3 ~ H CH3
2.13: Cl Cl~ CH3 : CH3 H
/~fiO79 2;10 5 2 7 8 PCI/EP93/00171
.
- 28 -
Table 3: Intermediates of the ~orrnula
- ' ,
R1
~;' "' `' ~C~O ' ' ` . " ' ''~
` ' , ' O ~o '' ' . ' ' '':
.
;` . Comp. No. Rl Z Physical data
~ ,. . .
3.01 H NO2 m.p. 59-63C
3.02 H NH2 m.p. 121-122C
3.û3 Cl NO2 m.p. 125-12B~C
3.04 Cl NH2 m.p. 78-79C
3'05 CH3 NO2 m.p. 78-80C
3.06 CH3 NH2 m.p. 90-92C
3.Q7 C2Hs NH2 n25 1.5683
3.08 C2Hs NO2 m p 64-65C
. . ' . : , ,' ......
Biological examPles
Exam~le B 1: Herbicidal activitv. preemer~ence
In~ a greenhouse, test plants are sown into seed dishes, and the soil surface is immediately
afterwards ~reated with an aqueous spray mixture prepa~d with a suspension concentrate
~muladon Example No. lO) corresponding to an application rate of 4 kg or 0.5 kg of
ac~ve ingredient/hectare. The seed dishes are kept in the greenhouse at 22-25C iand
50-70% relative atmospheric humidity.
After 3 weeks, the herbicidal activity is assessed using a nine-step radng system (I - to;al
damage, 9 = no action) by compiarison with an untreated control igroup.
Ratings from 1 to 4 (in particular l~ to 3) suggest a good to very good her~icidal activity.
Ratings from 6 to 9 (in particuiar from 7 to 9) suggest a good tolerance (in partieular in the
case of crop plants).
93~16079 21~ ~ 2 7 8 PCr/EP93/00171
' .
. - 29 -
-
Test plants: Avena, Setaria, Sinapis and Stellaria
:.
In this test, the compounds of the fonnula I according to the examples in Tables 1 and 2
show a powerful her~aicidal activity.
: . ' : .'
. . The s~me ~sults are obtained when the abovemen~oned aqueous spray mixture isprepared with an emulsion concentra~e (Formuladon Examples Nos. 1 and 6), solutions ::
~ : (Pormulation Example No. 2), granul~s (Folmula~on Example No~ 3), dusts (Formulation
~` . Examples Nos. 4 and 7), wettable powders (Formuladon Exarnple No. 5), extruder
granules and coated granules ~Formulation Examples Nos. 8 and 9).
. . .
: Table B1 shows examples of the good herbicidal activity of the compounds of the ~ormula
~ . .
,. . 1.......................................................... "
: , . .
Table Bl- Preeme~gence acdon
. . . .
. Test plants: .
Comp.No. Dosage Avena Seearia Sina- Stellar
rate pis ria
: [kg of
A~a]
, . . . _ .
.'` l.ûl 0.5 4 7 4 3
- ..1.0:~ 0.5 2 1 2
1.~3 4.0 6 3 3 2
. . 1.04 4.0 2 1 2 . 2
. . l.05 0-5 9 7 7 3
:: 1.06 0.5 3 2 2 2
';: . 1.07 0.5 ~ 2 2 2
i.' ~.08 0.5 1 1 1 2
0.5 2 2 2 2
~' . i.20 0.5 ~ 4 4 2 3
'' . . -
Examp e B2- Herbicidal activitY. Postemer~ence (contact herbicide)
A~ter emergence, a number of monocotyledon and dicotyledon weeds (in the ~ to ~leaf : -
s~g~) are ~prayed with an aqueous dispersion of acdve ingredient which has been
~, : . . .. ..
~ 93/16079 210 ~ 2 7 ~ Pcr/EP93/ool7l
- 30-
`
prepared with a suspension concentrate (Formulation Example No. 10) a~ a dosage rate of
4 kg and 05 kg OI active ingredient per hectare, and the plants are kept at 24-26~C and
45-60% relative atmospheric humidity. l~ days after the treatrnent, the herbicidal ac~vity
is assessed using a nine-step Mdng system (1 = total d~mage, 9 = no action) in companson
with an untreated con~ol group.
. . . .
- Test plants: Avena, Setaria, Sinapis and Stellaria.
.
In this test too, the compounds of the forrnula I according to the examples in Tables 1 and
2 show a good herbicidal activity. ;
~., . ' ' . ` ' .
- - The same results are obtained when the abov~nentioned aqueous spray mixture is
prepared with an emulsion concen~ate (Forrnula~on Examples Nos. 1 and 6), solutions
(Fonnulation Examp}e No. 2), granules (Formulation Example No. 3), dusts (Formulation
~3xamples Nos. 4 and 7), wettable powders (Folmulation Exarnple No. 5), extrudergranules and coated granules (Formulation Examples Nos. 8 and 9).
.. . . . .
Table B2 shows examples of the good herbicidal aclivity of the compounds of the formula
.1 I.
. ~, , .
., ~ . . .
: .
.~ . ~ .
~', ' . . ~' ' ` .. ,
.
... .
~J
. .~ . .
.~ .
.1 . . ` ` :
,$
'.`1 , . . . .
, i ~ . . !
1 ` - . . ` ` .
'~ ' ' ~, ` ` '
~i: , ' : ' ' . .
';i ' ' '` :
~-';, ' ~ , ,:,
~ ' " `.` ' :'
J~ 79 2 ~ 0 5 2 7 ~ P~r/EPg3/aol7~
`
- 31 -
Table B2: Postemergence action
., .
Test plan~
Comp.No. Dosage Avena Setaria Sina- Stella-
rate pis r~a
[kg of
AVha
.
1.01 0.5 S 8 3 3
1.02 0.5 1 2 2
1.03 4.0 7 7 3 5
1.0~ 4.0 1 3 2
1.~5 O.S 9 8 3 4
1.G36 0.5 5 5 2 2
1.07 0.5 3 7 2 2
I.08 0.~ 1 2 1 2
1.15 0.5 2 3
1.20 0.5 5 4 1 2
.. ~ ,
" -.
' x~ple B3. Herbicidal acdvitY in padd~ rice; The aquatlc weeds Echinochloa crus-gaIli
I~ and Monochoria vag. are sown in plaseic beakers ~surface area 6ZZ3 cm2, volume 500 ml~.
After sowing, the beakers a~ filled with water to the soil surface. 3 days after sowing, the
; water level is raised just above ~e soil sur~ace (3-5 mm). Applicauon is effected 3 days
after~ sowing by spraying ~he ~est substances onto the containers. The dosage rate used
corresponds tO an amount of 8-500 g of active ing~edient per hectare. The beakers with the -~
p!ants are then placed in a greenhouse under optimum growth conditions for the ~ice
- weeds, i.e. at 25-30C and high aZ~mospheric humidi~y. `
~ . .
- 3 weeks after application, the tests aIe evaluated. The compounds of the forrnula I haYe a ~ -
- ~ damZaging effect on the weZ~ds.
s i - : .
3 ~
.
,. ., .. : ,
:. ~
. ~
