Note: Descriptions are shown in the official language in which they were submitted.
2 ~
O.Z. OOS0/40666
Herbicidal and lant arowth re~ulatin~
azolylmathyloxirane~
The present invention ralate~ ~o the u~e of
azolylmethyloxiranes of the g~neral formula I
1~7 ,, I
H~_~N-CH-C - CHR3
Rl R2
whers
Rl i~ hydrogen or halogen,
R~ and ~3 are each C1-C8-alkyl which may carry one of the
: following radical~s dioxanyl or phe~yl, where th~ phenyl
: 10 radioal in turn may carry from one to fi~e halogan atoms
~ and/or rom one to three of th~ following group~: C1 C4-
:; alkyl, Cl~C~-haloalkyl, C~-C4-alkoxy and~or Cl-C4-halo-
alkoxy,
C3-Ca-cyclo~lkyl, C5-Ca-cycloalkenyl, tetrahydropyranyl or
norhornyl, whQx~ the~e cyclic xadicals may carry from 1
to 3 of the following ~ubstituent~s Cl-C4-alkyl andJor
halogen,
phenyl~ biphenyl, naphthy} or pyridyl, where these
aromatic radical~ may carry from one to five halogen
atoms and/or from:one ~o ~hree of the following ~ub~titu-
ent~: cl C4-alXyl ~ C~-C4-haloalkyl, C1-C4-alkoxy, Cl-C4-
haloalko ~, pheno~y, phenyl~ulfonyl~ amino, C~-C~-al ~1-
: amino, di-C~-C4-alkylamino and~or nitro, and
X i~ nitrog~n or a methin~ group CN,
or ~heir agriculturally u3able ~alts a~ herbicide~, the
u~e o~ azolylmethyloxiranas of the general formula I,
where Rl i3 not hydrogen, as plan~ grow~h-regu:Latin~
agent~ and methods ~or using ~he herbicidal and plant
growth-regulating agent~.
DE-A 3 536 529, DE-A 3 825 814 and EP-A 95 564 describe the
azolylmethylo~iranas ~ dainad at the outse~, a~ fungi-
cidea. Furthermore~ EP-A 315 850 de~cribe~ the azolyl-
me~hy}o~iranss ds~ined a~ the outset, in which Rl is
hydrogen, a~ growth regulatore.
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2 ~
- 2 - 0.~. OQ50/~0666
It i~ an object of the pre~en~ invention to pro-
vide novel her~icidal and plan~ growth-regula~ing agent~.
We have found th~t this object i~ achieved and
thak azolylmethyloxiranes are suitabl~ both for control-
ling undesirablQ plant growth and for influencing plantgrowth.
~ ha a~olylme~hyloxiranes I are obtained by
generally known methods (for example DE-A 3 563 529 and
EP-A 94 564~.
Compound~ I in which R~ is halogen are par-
ticularly advantageously obtained by reacting an epoxy
aldehyde II with an N-m thylazole derivative III in the
pre ence of a halogena~ing agent (Hal),
X / \ [Hal] ~ ¦ / \
~1 + OHt:~C--CHR 3 --` N~N--CH C--CHR 3
N~ NH I 2 Rl R 2
III II I
Suita~le halogenating agent~ are pho~phorus
halide~, ~uch a~ phosphoru3 trichloride, pho~phorus tri-
bromide or pho~phoru~ pentachlorida, a~ well as pho~
phorus oxyhalide~, suoh a~ pho~phorus oxytrichloride, and
thionyl h~lide~, such as thionyl chloride and thionyl
bromide.
The reaction is u~ually carried out in the
pre~snce or ab~ence of an aprotic organic ~olvent at from
-30 to 80C, in particular from O to 30~C.
It is preferably carri~d out in the absence of a
~olv~nt or in aprotic solvent~, such as pentane, hexane,
decalin, toluene, methylene chloridet chloroform, carbon
t0~rachloride, dichloroethane or corresponding mixture~
The compound~ of the formula I contain a~ymmetric
carbon atom~ and can therefore oocur a~ enantiomers and
dia~tereomer~. In the ca~e of the novel compound~, the
mixture~ of dia~tereomers can bo separated in a conven~
tional manner, for example on the basi~ of their dif-
~erenk solubilitie~ or by column chromatography, and can
be i~olatod in pure form. The racema~es of the novel
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2~3~
- 3 - O.Z. 0050/40666
compounds can be separated by known methods, for example
by salt formation with an op~ically ~ctive acid, separa-
tion of the diastereomeric salts and liberation of the
enantiomer~ by means of a base. Both the pure diastereo-
mers or enantiomers and their mixtures obtained in thesynthesis are suitable a~ herbicidal or growth-regulating
agents.
Addition salts with acids are, for example, the
hydrochlorides, bromides, sulfates, nitrate~, phosphates,
oxalates or dodecylbenzen~sulfonates. The activity of
the salts i~ due to the cation, so that the anion i~ in
general unimportant. The novel actlve ingredient salts
are prepared by reacting the azolylmethyloxiranes with
the acid~.
lS With regard to their use a~ herbicide~, par-
ticularly suitable azolylmethyloxiranes I are tho3e in
which ths ~ubstituent ha~e the following meanlng-~:
R1 is hydrogen or halogen, ~uch a~ fluorine, chlorine~
bromine or iodine, in particular hydrogen, chlorine or
~ 20 bromine,
- R2 is alkyl, ~uoh as methyl, ethyll propyl, 1-methylethyl,
butyl, l-methylpropyl, 2-m~hylpropyl, l,l-dimethylethyl,
pentyl, l-methylbutyl, 2-methylbutyl, 3-methylbutyl,
dLmethylpropyl, 1,2-dimethylpropyl, 2,2-dimethyl-
propyl, 1-ethylpropyl, hexyl, l-methylpentyl, 2-methyl-
: pentyl, 3-methylpentyl, 4-methylpentyl, l,l-dimethyl-
butyl~ 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethy-
lbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, l-ethyl-
butyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-tri-
methylpropyl, l-ethyl-l-methylpropyl or 1-ethyl-2-methyl-
propyl, in particular l-methylethyl or l,l-dimethylethyl,
where this alkyl group may be substituted, preferably in
the 1-, 2- or 3-position, by one o the follawing radi
cals~ 1,3-dioxan-2-yl, 1,3-dioxan-4 yl, 1,3-dioxan-5-yl
or 1,3-dioxan-2-yl, in particular 1,3-dioxan-2-yl, or
phenyl which in turn may car.ry Prom one ~o five of the
halogen atom~ stated under Rl and/or from one to three of
: , . .
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2 ;3 ~
4 - O.Z. 00~0/40665
the following groups: alkyl of 1 to 4 carbon atom~ as
stated above, in particular methyl, especially phenyl,
haloalkyl, such as fluoromethyl, di1uoromathyl, tri-
fluoromethyl,chlorodifluoromethyl,dichlorofluoxomethyl,
S trichloromethyl, 1-fluoroethyl, 2~fluoroethyl, 2,2~
di1uoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2,2-di-
fluoroethyl,2,2-dichloro-2-fluoroethyl,2,2,2-trichloro-
ethyl or pentafluoroethyl, in particular ~rifluoromethyl,
alkoxy, such as methoxy, ethoxy~ propoxy, 1-methyletho~y,
butoxy, l-methylpropo~y, 2-methylpropoxy or l,l-dimethyl-
etho~y, in particular methoxy, and/or haloalkoxy, such a~
difluoromethoxy,trifluoromethoxy,chlorodifluoromethoxy,
: dichlorofluoromethoxy, 1-fluoroethoxy, 2-fluoxoethoxy,
2,2-difluoro~thoxy, 1~1,2,2-tetrafluoroethoxy, 2,2,2-
trifluoroethoxy, 2-chloxo-1,1,2-trifluoroethoxy or penta-
fluoroethoxyl in particular trifluoromethoxy,
cycloalkyl, such a~ cyclopropyl, cyclobutylr c~clopentyl,
~ cyclohe~yl, cycloheptyl or cyclooctyl, in parti.cular
;;~ cyclohexyl,
cycloalkenyl, suoh as l-cyclopentenyl, ~-cyclopentenyl,
3-cyclopentenyl, l-cyolohexenyl, 2-cyclohexenyl, 3-cyclo-
hexenyl/ 1-cyoloheptenyl, 2-cyclohept3nyl, 3-cyclohepten-
;~ yl, 4-cycloheptenyl, 1-cyclooctenyl, 2-cyclooctenyl, 3-
cyclooctenyl or 4-cyclooctenyl~ in particular 3-cyclo-
hexenyl,
~ tetrahydropyranyl, such as 2-tetrahydropyranyl, 3-tetra-
: hydropyranyl or 4-tetrahydropyranyl, in particular 4-
tetxahydropyranyl,
norbornyl, such a~ 2-norbornyl,
whore the abovementioned cyclic radicals may carry from
one to thrae o~ the abo~ementioned alkyl groups, in par-
ticular methyl, and/or halogen, ~uch a~ fluorine, chlor-
in~ or bromine, in particular chlorine or bromine;
phenyl, biphe~yl, naph~hyl or pyridyl, where these
aromatic radical~ may carry from one to five halogen
atoms a~ ~ta~.ed under Rl, in particular chlorine or
bromine, and~or from 1 to 3 o the following
:: . ' , ' - " ''' ~ -' '
' ~ ' ' ' ~ . .
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2~.L~3~a
- 5 ~ O.Z. 0050/40666
sub~tituent~:
alkyl as stated abo~e, in particular methyl,
haloalkyl a~ stated abo~a, in particular trifluoromethyl
or difluoromethyl,
alkoxy a~ stated above, in particular methoxy,
haloalkoxy a stated above, in particular trifluorometh-
oxy~
phenoxy, phenylsulfonyl, amino, nitro or alkylamino, such
as methylamino, ethyl~mino, propylamino, 1-methylethyl-
amino, butylamino, l-methylpropylamino~ 2 methylpropyl-
amino or l,l-dLmethylethyl~mino, in particular nitro or
amino and/or
dialkyl~mino, such as dLmethy].amino, diethylamino, di
propylamino, di-(l methylethyl) amino, dibutylamino, di-
(l-methylpropyl)-amino, di (2-methylpropyl)-amino or di-
(l,l-dim~thylethyl)-amino, in particular dimethylamino,
R3 i~ ln general and in particular the radical ~ta~ed
under R2 and
X i~ nitrogen or a methine group CH.
With regard to their u~e as plant growth regula-
tor~, particularly suitabla azolylmeth~loxirane~ I are
tho3e in which ths ~ubs~ituant~ have the following mean-
ingR
R1 is halogen, in particular chlorine or bromine,
R2 is alkyl, in particular methyl, 1-~eth~lsthyl or 1,1-
dimethylethyl,
where thi3 alkyl group may be ~ub~titu~ed, preferably in
the 1- or 2-po~ition, by the following radical~s
phe~yl, biph~nyl, naphthyl or pyridyl, where these
aromatic radical3 may car~y from on~ to f iV9 halQg2n
atom~ as statad under R1, in particular chlorine or
bromine, and/or from one to thxee of the ~ollowin~ sub-
~tituents:
alkyl a~ ~tat~d above, in particular methyl,
haloalkyl a~ ~tated abo~e, in particular tri1uoromethyl
or di~luorQmethyl,
alkoxy a~ stated above, in particular mo~hoxy or
2~2~
6 O.Z. 0~50/4066
haloalkoxy as stated above, in particular trifluoromethoxy,
R3 is in particular the radical stated above for R2 and
X is in particular nitrogen or a methine group CH.
5 The azolylmethyloxiranes I, or the herbicidal and growth-regulating agents
containing the~, may be applied for instance in the form of directly
sprayable solutions, powders, suspensions (including high-percentage
aqueous, oily or other suspensions), dispersions, emulsions, oil dis-
persions, pastes, dusts, broadcasting agents, or granules by spraying,
10 atomizing, dusting, broadcasting or watering. The forms of application
depend entirely on the purpose for which the agents are being used, but
they must ensure as fine a distribution of the active ingredients accord-
ing to the invention as possible.
15 For the preparation of solutions, emulsions, pastes and oil dispersions to
be sprayed direct, mineral oil fractions of medium to high boiling point,
such as kerosene or diesel oil, further coal-tar oils, and oils of vege-
table or animal origin, aliphatic, cyclic and aromatic hydrocarbons such
as toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphtha-
20 lenes and their derivatives such as methanol, ethanol, propanol, butanol,chloroform, carbon tetrachloride, cyclohexanol, cyclohexanone, chloro-
benzenet isophorone, etc., and strongly polar solvents such as N,N-di-
methylformamide, dimethyl sulfoxide, N-methylpyrrolidone, water, etc. are
suitable.
Aqueous formulations may be prepared from emulsion concentrates, pastes,
dispersions, wettable powders or water-dispersible granules by adding
water. To prepare e~ulsions, pastes and oil dispersions the ingredients as
such or dissolved in an oil or solvent may be homogenized in water by
30 means of wetting or dispersing agents, adherents or emulsifiers. Concen-
trates which are suitable for dilution with water may be prepared from
active ingredient, wet~ing agent, adherent, emulsifying or dispersing
agent and possibty solvent or oil.
35 Examples of surfactants are: alkali metal, alkaline earth metal and
ammonium salts of ligninsulfonic acid, naphthalenesulfonic acids,
phenolsulfonic acids, alkylaryl sulfonates, alkyl sulfates, and alkyl
sulfonat&s, alkali metal and alkaline earth metal salts of dibutyl-
naphthalenesulfonic acid, lauryl ether sulfate, fatty alcohol sulfates,
40 alkali metal and alkaline earth metal salts of fatty acids, salts of
sulfated he~adecanols, heptadecanols, and oc~adecanols, salts of sulfated
fatty alcohol glycol ethers, condansation products of sulfonated
naphthaiene and naphthalene derivatives With formaldehyde, condensation
products of naphthalene or naphthalenesulfonic acids with phenol and
formaldehyde, polyoxyethylene octylphenol ethers, ethoxylated isooctyl-
phenol, ethoxylated octylphenol and ethoxylated nonylphenol, alkylphenol
; polyglycol ethers, tributylphenyl polyglycol ethers, alkylaryl polyether
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7 O.Z. 0050/40666
alcohols, isotridecyl alcohol, fatty alcohol ethylen~ oxide condensates,
ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated poly-
oxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol esters,
lignin, sulfite waste liquors and methyl cellulose.
The formulations contain from 0.1 to 95, and preferably 0.5 to 90, YO by
weight of active ingredient. Ths active ingredients are employed in a
purity of from 95 to 100~ (according to the NMR spectrum).
10 The compounds I according to the invention may be formulated for instance
as follows:
T. 90 parts by weight of compound no. 109 is mixed with 10 parts by
weight of N-methyl-alpha-pyrrolidone. A mixture is obtained which is
15 suitable for application in the form of very fine drops.
II. 20 parts by weight of compound no. 117 is dissolv~d in a mixture con-
sisting of 80 parts by weight of xylene, 10 parts by weight of the adduct
of 8 to 10 moles of ethylene oxide and 1 mole of oleic acid-N-monoethanol-
20 amide, 5 parts by weight of the calcium salt of dodecylbenzenesulfonicacid, and 5 parts by weight of the adduct of 40 moles of ethylene oxide
and 1 mole of castor oil. By pouring the solution into 100,000 parts by
weight of water and uniformly distributing it therein, an aqueous disper-
sion is obtained containing 0.02% by weight of the active ingredient.
2~
III. 20 parts by weight of compound no. 115 is dissolved in a mixture
consisting of 40 parts by weight of cyclohexanone, 30 parts by weight of
isobutanol, 20 parts by weight of the adduct oF 7 moles of ethylene oxide
and 1 mole of isooctylphenol, and 10 parts by weight of the adduct of
30 40 moles of ethylene oxide and 1 mole of castor oil. By pouring the
solution into 100,000 parts by weight of water and finely distributing it
therein, an aqueous dispersion is obtailled containing 0.02% by weight of
the active ingredient.
35 IV. 20 parts by weight of compound no. 109 is dissolved in a mixture con-
sisting of 25 parts by weight of cyclohexanone, 65 parts by weight of a
mineral oit fraction having a boiling point between ~10 and 280C, and
10 parts by w0ight of the adduct of 40 moles of ethylene oxide and 1 mole
of castor oil. By pouring the solution into 100,000 parts by weight of
40 water and uniformly distributing it therein, an aqueous dispersion is
obtained containing 0.02% by weigt~t of the active ingredient.
V. 20 parts by weight of compound no. 110 is well ~ixed with 3 parts by
weigh~ of the sodium salt of diisobutylnaphthalene-alpha-sulfonic acid,
17 parts by weight of the sodium salt of a lignin-sulfonic acid obtained
from a sulfite waste liquor, and 60 parts by weight of powdered silica
gel, and triturate~ in a hammer mill. By uniformly distributing the
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8 O.Z. 0050/40666
mixture in 20,000 parts by weight of wa~er, a spray liquor is obtained
containing 0.1% by weight of the active ingredient.
VI. 3 parts by weight of compound no. 112 is intimately mixed with
5 97 parts by weight of particulate kaolin. A dust is obtained containing 3Y0
by weight of the active ingredient.
VII. 30 parts by weight of compound no. 117 is intimately mixed with a
mixture consisting of 92 parts by weight of powdered silica gel and
10 8 parts by weight of paraffin oil which has been sprayed onto the surface
of this silica gel. A formulation of the active ingredient is obtained
having good adherence.
VIII. 20 parts by weight of compound no. 116 is intimately mixed with
15 2 parts by weight of the calcium salt of dodecylbenzenesulfonic acid,
8 parts by weight of a fatty alcohol polyglycol ether, 2 parts by weight
of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate
and 68 parts by weight of a paraf~inic mineral oil. A stable oily
dispersion is obtained.
IX. 40 parts by weight of compound no. 109 is intimately mixed with
10 parts of the sodium salt of a phenolsulfonic acid-urea-formaldehyde
condensate, 2 parts of silica gel and 48 parts of water. A stable, aqueous
dispersion is obtained. Dilution in 100,000 parts by weight of water gives
25 an aqueous dispersion con~aining 0.04wt% of active ingredient.
Generally, the growth-regulating active ingredients are formulated as the
herbicidal active ingredients are.
30 Powders, dusts and broadcasting agents may be prepared by mixing or
grinding th~ ~ctive ingredients with a solid carrier.
Granules, e.g., coated, impregnated or homogeneous granules, may be
prepared by bonding the active ingredients ~o solid carriers. Examples of
35 solid carriers are mineral earths such as silicic acid, silica gels,
silicates, talc, kaolin, attapulyus clay, limestone, lime, chalk, bole,
loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium
sulfate, ~agnesium oxide, ground plastics, fertilizers such as ammonium
sulfate, ammonium phosphate, ammonium nitrate, and ureas, and vegetable
49 products such as grain flours, bark meal, wood meal, and nutshell meal,
eelluloslc powders, etc.
The form~lations, or the ready-to-use preparations prepared therefrom,
such as solutions, emulsions, suspensions, powders, dusts, pastes and
granules, are applied in conventional manner, for example pre- or
postemergence, or as seed dressings.
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9 O.Z. 0050/40666
If certain crop plants tolerate the active ingredients less well,
application techniques may be used in which the herbicidal agents are
sprayed from suitable equip~ent in such a manner that the leaves of
sensitive crop plants are if possible not touched, and the agents reach
5 the soil or the unwanted plants growing beneath the crop plants (post-
directed, lay-by treatment).
The application rates depend on the objective to be achieved, the time of
the year, the plants to be combated and their growth stage, and are from
10 0.001 to 5, preferably 0.01 to 3, kg of active inyredient per hectare.
In view of the numerous application methods possible, the compounds
according to the invention may be used in a large number of crops. rhose
which follow are given by way of example:
Botanical name Common name
Allium cepa onions
Ananas comosus pineapples
Arachis hypogaea peanuts ~groundnuts)
20 Asparagus officinalis asparagus
Avena sativa oats
; Beta vulgaris spp. altissima sugarbeets
Beta vulgaris spp. rapa fodder beets
Beta vulgaris spp. esculenta table beets, red beets
25 Brassica napus var. napus rapeseed
Brassica napus var. napobrassica swedes
Brassica napus var. rapa turnips
Brassica rapa var. silvestris
Camellia sinensiS tea plants
30 Carthamus tinctorius safflower
Carya illinoinensis pecan trees
Citrus limon lemons
Citrus maxima grapefruits
Citrus reticulata mandarins
3S Citrus sinensis orange trees
Coffea arabica (Coffea canephora,
Coffea liberical coffee plants
Cucumis melo melons
Cucumis sativus cucumbers
40 Cynodon dactylon Bermudagrass
Daucus carota carrots
Elais guineensis oil palms
Fragaria vesca strawberries
Glycine max soybeans
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O.Z. 0050/40666
Botanical name _ _ _ _ _ _ Common name
Gossypium hirsutum (Gossypium arboreum,
Gossypium herbaceum, Gossypium vitifolium) cotton
Helianthus annuus sunflowers
5 Helianthus tuberosus Jerusalem artichoke
Hevea brasiliensis rub~er plants
Hordeum vulgare barley
Humulus lupulus hops
Ipomoea batatas sweet potatoes
10 Juglans regia walnut trees
Lactuca sativa lettuce
Lens culinaris lentils
Linum usitatissimum flax
Lycopersicon Iycopersicum tomatoes
15 Malus spp. apple trees
Manihot esculenta cassavd
Medicago sativa alfalfa (lucerne
Mentha piperita peppermint
Musa spp. banana plants
20 Nicotiana tabacum (N. rustica) tobacco
Olea europaea olive trees
Oryza sativa rice
Panicum miliaceum millet
Phaseolus lunatus limabeans
25 Phaseolus mungo mungbeans
Phaseolus vulgaris snapbeans, green beans,
dry beans
Pennisetum glaucum pearl millet
Petroselinum crispum spp. tuberosum parsley
30 Picea abies Norway spruce
Abies alba fir trees
Pinus spp. pine trees
Pisum satlvum English peas
Prunus avium cherry trees
35 Prunus domestica plum trees
Prunus dulcis almond trees
Prunus persica peach trees
Pyrus communis pear trees
; Ribes sylvestre redcurrants
40 Ribes uva-crispa gooseberries
Ricinus communis castor-oil plants
Saccharum officinarum sugar cane
Secale cereale rye
Solanum tuberosum Irish potatoes
Sorghum bicolor (s. vulgare~ sorghum
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sotanical na~e Common name
Sorghum dochna sorgo
Spinacia oleracea spinach
Theobroma cacao cacao plants
5 Trifolium pratense red clover
Triticum aestivum wheat
Triticum durum durum wheat
vaccinium corymbosum blueberries
vaccinium vitis-idaea cranberries
10 Vicia faba tick beans
Vigna sinensis (V. unguiculata) cow peas
Vitis vinifera grapes
Zea mays Indian corn, sweet corn,
maize
The azolylmethyloxiranes of the general formula I in which R1 is not
hydrogen may exsrcise a variety of influences on practically all plant
development stages, and are therefore used as growth regulators. The
~iversity of action of growth regulators clepends especially on
a) plant type and variety;
~ b) the time applied, with reference to the development stage of the
; plants ancl the time of the year;
c) the place and me~hod of application (seed treatment, soil treatment,
or application to foliage);
d) climatic factors, e.g., average temperature, amount of precipitate,
sunshine and duration;
e) soil conditions (including fertili~ation);
f) the formulation of the active ingredient; and
30 9) the application rate and active i~gredient content of the agents.
:
A description of some of the various possibilities of using the yrowth
regulators according to the invention in agriculture and horticulture is
given below.
A. With the growth-regulating azolylmethyloxiranes (R1 $ ~), vegetative
plant growth can be inhibited to a considerable extent, a fact which
is manifested particularly in a reduction in plant height. The treated
plants thus have a compact habit; furthermore, the leaf color is
darker.
Of advantage in practice is for example the reduction in grass growth
on roadsides, hedges, canal embankments and on areas such as parks,
sportsgrounds, fruit orchards, lawns ancl airfields, thus reducing
expensive and time-consuming mowing.
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12 O.Z. 0050/40666
In woody ~ruit-bearing plants and other trees and shrubs, cost-
intensive pruning measures can be reduced.
A further feature of economic interest is the increase in the rigor of
crops which tend to lodge, such as cereals, Indian corn, sunflowers
and soybeans. The shortening and strengthening of the stem thus caused
reduces or eliminates the danger of lodging under unfavorable weather
conditions.
The use of growth regulators is also important for inhibiting plant
height and changing the time of ripening in cotton. It is thus pos-
sible for this important crop to be harvested completely mechanically.
The use of the compounds I (R1 $ H) may also increase or inhibit
lateral branching. This is of interest when, for instance in tol)acco
plants, it is desired to inhibit th0 formation of lateral shoots
~suckers) in favor of leaf development.
With compounds I, it is possible for instance in winter rape to con-
siderably increase the resistance to freeze injury. On the one hand,
upward growth and the development of a too luxuriant (and thus partic-
ulariy frost-susceptible~ leaf or plant mass are inhibited; on the
other, the young rape plants are kept, in spite of favorable growth
conditions, in the vegetative development stage before winter frosts
begin. The danger of freeze injury is thus eliminated in plants which
tend to lose prematurely their inhibition to bloom and pass into the
generative phase. In other crops, too, e.g., winter cereals, it is
advantageous if the plants are well tillered in the fall as a result
of treatment with the compounds according to the invention, but enter
winter with not too lush a growth. rhis is a preventive measure
ag3inst increased susceptibility to freeze injury and - because of the
relatively low leaf or plant mass - attack by various (especially
fungus) diseases. The inhibition of vegetative growth also makes
closer planting possible in numerous crops, which means an increase in
yield, based on the area cropped.
. Better yialds both of plant parts and plant materials may be obtained
with growth-regulating agents based on azolylmethyloxiranes I
(Rl ~ H). It is thus for instance possible to induce increased form-
ation of buds, btossoM, leaves~ fruit, seed grains, roots and tubers,to increase the sugar content of sugarbeets, sugarcane and citrus
fruit, to raise the protein content of cereals and soybeans, and to
stimulate the increased ~ormation of latex in rubber trees.
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13 O.Z. 0050/40666
The a~olylmethlyoxiranes I (Rl ~ H) may raise the yield by influencing
plant metabolism or by promoting or inhibiting vegetative and/or
generative plant growth.
5 C. It is also possible with the azolylrnethyloxiranes (R1 ~ H) to shorten
or lengthen growth stages and to accelerate or retard the ripening
process in plant parts either before or after harvesting.
A factor of economic interest is for example the facilitation of har-
vesting made possible by a chemical, temporally concentrated loosening
~abscission) of the adherence of stalks to the branches of citrus
fruit, olive trees, and other kinds of pomes, drupes and indehiscent
fruit. The same mechar,ism, i.~., promotion of the formation of separ-
ation layers between fruit or leaf and stem of the plant, is also
essential for a readily controllable defoliation of crop plants, e.g.,
cotton.
D. Further, transpiration in crop plants may be reduced with the azolyl-
methyloxiranes I (R1 $ H). This is particularly important for plants
growing in agricultural areas which are expensive to irrigate, e.g.,
in arid or semi-arid areas. Irrigation frequency can be reduced by
using the compounds according to the invention, making for lower
costs. As a result of the use of growth regulators, the water avail-
able can be better utilized, because, inter alia,
- the si~e of the stomata opening is reduced;
- a thicker epidermis and cuticle are formed;
- penetration of the soil by the roots is improved;
- the micro-climate in the stand is favorably influenced by the
more compact growth.
The active ingredients to be used in accordance with the invention may be
applied not only to the seed (as a disinfectant), but also to the soil,
i.e., via the roots, and to the foliage by spraying.
In ~iew of the good tolerance of compounds I (R1 ~ H) by crop plants, the
application rate may be varied within wide limits. When the compounds are
used for treating seed, amounts of from O.OOI to 50, and preferably from
0.01 to 1, g are generally required. For foliage and soil treatment, rates
40 of from 0.01 to 10, and preferably from 0.1 to 5, kg/ha are in general
sufficient.
'' . ' ~' -
~: . . ~ .
` ' ' , . :...................... :
2 ~
14 O.Z. 0050/40666
To increase the spectrum of action and to achieve synergistic effects, the
herbicidal and growth-regulating azolylmethyloxiranes I may be mixed and
applied together with numerous representatives of other herbicidal or
growth-regulating active ingredient groups. Examples of suitable com-
5 ponents are diazines, 4H-3,1-benzoxazine derivatives, benzothiadiazinones,
2,6-dinitroanilines, N-phenylcarbamates, thiolcarbamates, halocarboxylic
acids, triazines, a~ides, ureas, diphenyl ethers, triazinones, uracils,
benzofuran derivatives, cyclohexane-1,3-dione derivatives, quinolinecar-
boxylic acid derivatives, phenyloxy- or heteroaryloxy-phenylpropionic
10 acids and salts, esters and amides thereof, etc.
It may also be useful to apply the compounds I, either alone or in combin-
ation with other herbicides, in admixture with other crop protection
agents, e.g., agents for combating pests or phytopathogenic fungi or
15 bacteria. The compounds may also be mixed with solutions of mineral salts
used to remedy nutritional or trace element deficiencies. Non-phytotoxic
oils and oil concentrates may also be added.
The directions given in the synthesis examples below were used - after
20 appropriate modification of the starting materials - to obtain further
compounds I. The compounds t~lus obtained are listed with their physical
data in the t~bles below.
I. Manufacture of the starting materials
Procedure 1
E/Z-2-(4-Fluorophenyl)-3-(2-chlorophenyl)-propenal
4.2 g of sodium hydroxide in 30 ml of water is added to a solution of
35 9 of 2-chlorobenzaldehyde in 300 ml of methanol. The reaction
mixture is oooled to 1~C, and 36 g of 4-fluorophenylacetaldehyde is
quickly added, the temperature rlsing to 30-40C. The mixture is
stirred for 10 hours at 40C, and the crystals which precipitate out
are removed from the cooled reaction solution by suction filtration.
Procedure 2
cis-2-Formyl-2-(4-fluorophenyll-3-(2-chlorophenyl)-oxirane
I ml of concentrated sodium hydroxide solution is added to a solution
of 78.2 g of E-2-(4-fluorophenyl)-3-(2-chlorophenyl)-propenal in
300 ml of methanol. The reaction solution is stirred at 0C, and
20.5 g of hydrogen peroxide (about 50~ strength) is slowly dripped in,
the internal temperature not exceeding 30C. After all has been added,
:
2 ~3 ~. f d ~3 3 ~:3
15 O.Z. 0050/40666
the mixture is stirred for 6 hours at room temperature; subsequently,
100 ml of water is added and the emulsion which forms is shaken out
with methyl tert-butyl ether. The isolated organic phase is dried over
sodium sulfate and evaporated down. There is obtair,ed 52.5 g (63%) of
cis-2-formyl-2-(4-fluorophenyl)~3-~2-chlorophenyl)-oxirane.
Il. Manufacture of the end products
Example 1
At 0C and under a nitrogen blanket, 12.8 9 of thionyl chloride is
added to a solution of 29.7 9 of triazole in 150 ml of methylene
chloride. The ~ixture is then stirred for 30 minutes at room tempera-
ture, after which 20 9 of cis-2-formyl-2-(4-fluorophenyl~-3-(2-chloro-
phenyl)-oxirane is added. After the reaction mixture has been stirred
for 12 to 15 hours at room temperature, 100 ml of water is added and
the organ;c phase is separated. The aqueous phase remaining is ex- ?
tracted twice with methylene chloride and the combined organic phases
are washed twice with saturated sodium bicarbonate solution. The iso-
lated organic phase is then dried over sodium sulfate and evaporated
down, giving 23.7 g ~85%) of cis-2-~1-(1-,2,4-triazol-1-yl)--1-chloro-
methyl]-2-t4-fluorophenyl)-3-(2-chlorophenyl)-oxirane as a 2:1 dia-
stereomer mixture. 5.8 g of the diastereomer A predominantly formed
; (m.p.: 152-156C; compound no. 106) is obtained from methyl tert-butyl
Z5 ether.
Example 2
At 0C and under a nitrogen blanket, 11.2 9 of thionyl bromide is
added to a solution of 14.9 g of triazole in 75 ml of methylene chlor-
; ide. The mixture is then stirred for 30 minutes at room temperature,
and lO g of cis-2-formyl-2-~4~fluorophenyl)-3-(2-chlorophenyl)-oxirane
is then added. After the reaction mixture has been stirred for 12 to
15 hours at room temperature, 100 ml of water is added to the solution
and the organic phase is separated. The aqueous phase remaining is ex-
tracted twice with methylene chloride and the combined organic phases
are washed twice with saturated sodium bicarbonate solution. The iso-
; lated organic phase is then dried over sodium sulfate and evaporated
down, giving 10.5 g (72~) of cis-2-tl-(1,2,4-triazol-1-yl)-1-bromo-
methyl]-2-(4-fluorophenyl)-3-(2-chlorophenyl)-oxirane as a 2:1 dia-
stereomer mixture. 3.5 g of the diastereomer A predominantly formed
(m.p.: 151-155C; compound no. 108) is obtained from methyl tert-butyl
ether.
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27 O.Z. 0050/40666
Use examples
The herbicidal action of the azolylmethyloxiranes of the formula I is
demonstrated in the following greenhouse experiments:
The vessels employed were plastic flowerpots having a volume of 300 cm3
and filled with a sandy loam containing about 3.0% humus. The seeds of the
test plants were sown separately, according to species.
10 In the preemergence treatment, the formulated active ingredients were
applied to the sur~ace of the soil immediately after the seeds had been
sown. The compounds were emulsified or suspended in water as vehicle, and
sprayed through finely distributing nozzles. After the agents had been ap-
plied, the vessels were lightly sprinkler-irrigated to induce germination
15 and yrowth. Transparent plastic covers were then placed on the vessels
until the plants had taken root. The cover ensured uniform germination of
the plants, insofar as this was no~ impaired by the active ingredients.
In the postemergence treatment, the plants were grown, depending on growth
20 form, to a height of 3 to 15 cm before being treated with the active
ingredients which were emulsified or suspended in water. The application
rate ~or postemergence treatment was 2.0 kg/ha.
The pots were set up in the greenhouse, species from warmer climates in25 warmer areas (20 to 35C) and species from moderate climates at 10 to
25C. The experiments were run ~or from 2 to 4 weeks. During this time the
plants were tended and their reactions to the various treatments assessed.
The assessment scale was 0 to 100, 100 denoting nonemergence or complete
30 destruction of at least the visible plant parts, and O denoting no damage
or normal growth.
The ptants used in the greenhouse experiments were as follows:
35 Abbrev. Biological name Common name _
CHEAL Chenopodium album lambsquarters (goosefoot)
GALAP Galium aparine catchweed bedstraw
SOLNI Solanum nigrum black nightshade
40 Compound no. 176, applied postemergence at a rate of 2.0 kg/ha, combated
unwanted broadleaved plants very well.
, ' '
28 O . Z . 0050/40666
To determine the growth-regulating proper~ies of the candidate compounds,
they were sprayed postemergence as aqueous formulations. The plants were
grown in plastic pots (approx. 12.5 cm in diameter and having a volume of
approx. 500 ml) in a substrate provided with sufficient nutrients. The
5 growth-regulating action observed was confirmed at the end of the experi-
ment by measuring the height of the plants. The figures obtained were
compared with the growth height of the untreated plants.
The reduction in growth height was also accompanied by a deepsr leaf col-
10 oration. The increased chlorophyll content is indicative of an increased
rate of photosynthe~is, making for bigger yields.
The growth-regulating action of the azolylmethyloxiranes (p1 ~ H) is
apparent from the following tables. For comparison purposes, chlormequat
15 chloride (CCC) was tested parallel to the azolylmethyloxiranes:
fH3
CH3-+l_CH2_CH2_Cl Cl~
CH3
~hlormequat chloride (CCC~
Table 1
20 Influence on the yrowth height of spring rape ("Petranova" variety) on
postemergence (leaf) treatmer.t
Example mg a.i./vessel Relative growth height
No. _ _ _ __ in ~0
2~
109 6 78.3
110 6 ~0.4
112 6 74.4
113 6 88.4
30 115 6 79.0
116 6 72.9
117 6 85.1
CCC ~ 93.2
35 * based on untreated plants
2 ~
890053
29 O.Z. 0050/~0666
Table 2
Influence on the growth height of soybeans ("Maple Arrow" variety~ on
postemergence (leaf) treat~ent
Example mg a.i./vessel Relative growth height
No in %
CCC 1.5 93.9
10 110 1.5 85.7
* based on untreated plants
Table 3
Influence on the growth height of spring barley ("Aramirl' variety) on pre-
emergence (soil) treatment
Example mg a.i./vessel Relative growth height
20 N_ _ %
CCC 6 83.4
189 6 77.0
25 * based on untreated plants
Table 4
Influence on the growth height of sunflowers ("Spanners Al17weck" variety)
30 on postemergence (leaf) treatment
Example mg a.i./vessel Relative growth height
No. _ _ _ in %
35 CCC 6 83.1
189 6 77.8
* based on untrQated plants
2 ~ 3 ~
890053
O.Z. 0050/40666
Table 5
Influence on the growth height of spring rape ("Petranova" variety) on
postemergence (leaf) treatment
Example mg a.i./vessel Relative growth height
~O. in %
_
CCC 6 92.2
lO 181 6 75.4
182 6 79.0
188 6 7g.2
189 6 75.3
15 * based on untreated plants
Table 6
Influence on the growth height of soybeans ("Labrador" varietyl on post-
20 emergence (leaf) treatment
Example mg a.i./vessel ~elatiYe growth height
No.
25 CCC 0.5 98.3
1.5 92.2
189 0.5 86.2
1.5 83.7
i
3~ * based on untreated plants
The plants used in the tests given in the tables were wheat (Triticum
aestivum), barley (Hordeum vulgare), rice (Oryza sativa), sunflowers
(Helianthus annuus), rape (Brassica napus) and soybeans ~Glycine max.).
' ' ~: ~ ' ' .~; ;
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