CA1238639A - 1-diazole- or 1-triazole-2, 3-diphenylpropane compounds as herbicides and growth regulators - Google Patents

Abstract

5-14688/=

1-Diazole- or 1-triazole-2,3-diphenylpropane compounds as herbicides and growth regulators Abstract of the Disclosure The invention relates to novel 1-diazolyl- or 1-criazolyl-2,3-di-phenylpropane compounds and derivatives thereof of the formula I

(I), wherein E is a nitrogen atom or the methine group -CH=, m and m' are each independently of the other 0, 1, 2 or 3, R and R' are each independently of the other halogen, C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxy, C1-C4haloalkoxy, nitro, cyano,C1-C4-alkylthio, phenyl or phenoxy, each unsubstituted or substituted by R(m), or are C1-C4alkoxycarbonyl, C1-C4haloalkylthio, amino, mono- or di(C1-C4alkyl)amino, R1 and R2 are each independently of the other hydrogen or C1-C4alk-yl, R3 and R4 are each independently of the other hydrogen, Cl-C4alkyl, C1-C4alkylcarbonyl or, when taken together, are a methylene bridge -CR6R7-, R5 is hydrogen or C1-C4alkyl, and R6 and R7, together with the carbon atom to which they are attached, are a 3- to 6-membered saturated or unsaturated hydrocarbon ring.

These compounds have herbicidal and plant growth regulating properties.

Description

~ 3~ 21489-6645 l-Diazole- or l-triazole-2 ~-di~e ~ )pane cc~pounds as herbicides and ~rowth regulators The present invention relate~ to noYel l-diazole- or l-triazole-2,3-diphenylpropane-2,3-diols and derivstives of the formula I below and to herbicidal and plant growth regulating compositions which contain these compounds. The invention al30 relates to the preparation of these novel l-diazole- or l-triazole-2,3-diphenylpropane-2,3-diol~
and of the compositions containing them, as well a~ to the use thereof for controlling weed~ and regulating plant growth.

Specifically, the invention relates to novel l-diazole- or l-tri-azole-2,3-diphenylpropane compounds and derivatives thereof, of the formula I
D-P OR OR c-~

G------C~
)~ / I I \ )~
~ Rs (R)m R~--C--R2 ( )m' / \
E .
Il 11 ~a wherein E is a nitrogen atom or the methine group -CH=, m and m' are each independentIy of the other 0, 1, 2 or 3, R and R' are each independently of the other halogen, Cl-C4alkyl, Cl-C4haloalkyl, Cl-C4alkoxy, Cl-C4haloalkoxy, nitro, cyano, Cl-C4alkylthio, phenyl or phenoxy, each unsubstituted or ~ub-stituted by R( ); or are Cl-C4alkoxycarbonyl, Cl--C4h~10alkylthio, amino, mono- or di(Cl-C4alkyl)amino, q~

~ 3~3~ 21489-66~5 Rl and R2 are each independently of the other hydrogen or Cl-C4-alkyl, R3 and R4 are each independently of the other hydrogen, Cl-C4alkyl, Cl-C4alkylcarbonyl or, when taken together, are a methylene bridge CR R -R5 is hydrogen or Cl-C~alkyl, and R6 and R7 are each independently of the other hydrogen or Cl-C4alkyl or, together with the carbon atom to which they are attached, are a 3- to 6-membered satur2ted or unsaturated hydrocarbon ring.

Depending on the indicated number of carbon atoms, alkyl by i~self or as moiety of another substituent denotes the following groups:
methyl, athyl, n-propyl, isopropyl, n-butyl, i~obutyl, sec-butyl and tert-butyl.

Halogen in the above definition signifies fluorine, bromine and iodine, with chlorine and bromine being preferred.

A molecular fragment -CR6R7 formed by R3 and R4 i9 a 1,3-dioxolane ring. A saturated or unsaturated hydrocarbon ring formed by -CR6R7 may be for example cyclopropyl, cyclobutyl, cyclopentyl, cyclo-pentenyl, cyclopentadienyl, cyclohexyl, cyclohe~enyl or cyclo-hexadienyl.

The compounds of fonmula I are oils, resins or, preferably, solids which are stable at room temperature and have u~eful herbicidal and plant growth regulating properties. They can be used for controlling undesirable weeds, for example in crops of useful plants, and for regulating plant growth.

Preferred l-diazole- or l-t~ia~ole-2,3-diphenylpropane oompounds are those - of the formula Ia ~L2~ ;39 // ~ I I // ~
C G~ (Ia), ~ Rs (R) CH (R') , m 1 2 m N
E
Il 11 ~ N

wherein E, m, m', R, R', R3, R~ and R5 are as defined for formula I;
- of the formula Ib -- OH OH -~
// ~ I I // ~
t ^--G-~ -CH-~ ~ (Ib), ~ Rs (R)m ICH2 (R~m, N
N
Il 11 -- N

wherein each of m and m'independently is O, 1 or 2, and each of R
and R' independently of the other is halogen, Cl-C4alkylj Cl-C4-alkoxy or Cl-C4haloalkyl, in particular

2-(2,4-dichlorophenyl)-3-phenyl-1-(1,2,4-triazol-lH-l-yl)-propane-2,3-diol, 2-(4-chlorophenyl)-3-phenyl-1-(1,2~4-triazol-lH-l-yl)-propane-2,3-diol, 2-(4-chlorophenyl)-3-(2-chlorophenyl)-1-(1,2,4-triazol-lH-l-yl)-propane-2,3-diol, 2-(4-chlorophenyl)-3-para-tolyl-1-(1,2,4-triazol-lH-l-yl)-propane 2,3-diol 2-(4-chlorophenyl)-3-(4-methoxyphenyl)-1-(1,2,4-triazol-lH-l-yl)-propane-2,3-diol and , ~ ~
. ~

. ' '~ ,"

~3i3~39 2-(4-chlorophenyl)-3-(4-fluorophenyl)-1-(1,3,4-tria~ol-lH-l-yl)-propane-2,3-diol;

- of the formula Ic o-- OH OH --// ~ I I // ~
~ {}--C~o O (Ic), (R) CH (R') , m 1 2 m N

/ \il i1 --N

wherein each of m and m'independently is O, 1 or 2 and each of R and R' independently of the other is halogen, Cl-C4alkyl, Cl-C4alkoxy or Cl-C4haloalkYl;

- of the formula Id -- OR OR --

3 1 4 //
CH-- ~ (Id), )~ / I I \ ~
~ Rs (R) CH (R') , m 1 2 m N
N
Il 11 . N

wherein each of m and m' independently is O, 1 or 2, each of R and R' independently of the other is halogen, Cl-C4alkyl, Cl-C4alkoxy or Cl-C4haloalkyl, and each of R3 and R4 independently of the other is Cl-C4alkyl, Cl-C4alkylcarbonyl, or one of R3 and R4 is also hydrogen or both taken together form 8 3- to 6-membered alkylene bridge which may be substituted by one or two Cl-C4alkyl groups, in particular ~2~i39 2,2-dimethyl-4-phenyl-5-(2,4-dichlorophenyl)-3-(l,2,4-triazol-lH-l-ylmethyl)-l,3-dioxolane, or l-(l,3,4-triazol-lH-l-yl)-2-(2,4-di-chlorophenyl)-2-methoxy-3-phenyl-propan-3-ol.

The compounds of formula I are prepared by various synthesis pathways, some of which are known, for example as de~cribed in Canadian patent~ 1,210,409 and 1,215,374.

The compounds of formula I are prepared for example by reacting an ~-haloketone of formula II
-a H ~ o-~
R ~ I 11 // ~
~ G------C--- (II), )~ / I \ )( ~ Hal (R)m (R') with paraformaldehyde or with a ketone of the formula O-CRlR2 and a non-nucleophilic base, for example an alkali metal hydride (LiH, NaH, KH, K-tert-butylate or NaOC2H5), and subsequently adding an imidazole or l,2,4-triazole as such or in the form of an alkali metal salt to give an alcohol of formula III
o-- OH O --// ~ I 11 // ~
~ ~--C------C--- ~ (III), )~ / I I \ ~

(R)m Rl-C-R2 ( )m' ::
N
E c Il 11 .
N .

which is reacted by treatment with a complex hydride such a~ sodium borohydride, lithium aluminium hydride or a lithium alkyl compound LiR5 or with a magnesium halide R5MgHal, to ~ive the diol of formula IV, ~- :

. ;

~L~3~

-o OH OH ~~
// \\ I I ~/ ~
(IV), )~ / I I \ )~
~ Rs (R)m Rl--G--R2 (Rl)m, / \
E
Il 11 - N

wherein R3 and R~ are hydrogen.

If R5 is to be hydrogen the reaction can also be carried out with hydrogen and a hydrogenation catalyst.

The compounds of formula III can also be prepared by condensing a deoxybenzoin of the formula VI with an aldehyde or ketone oE the formula VI
o--- O --- o // ~ 11 // ~ 11 ---CH2-G~ (VI), + C (V~ > (VII) ~ / \ )~ /\ ' Rl R2 (R)m (Rl ) and then converting the resultant compound of formula VII

,,_. O
R ~ 11 // ~
o ---C~ --C- (VII), )~ / 11 \ )( / 0=- 9=0 \
~ (R)m / \ (R~)m~
-with a peracid or with hydrogen peroxide in the presence of a base, for example aqueous sodium hydroxide, into the corresponding epoxide of formula VIII

, '~
~' :

. - . o // ~ ll // ~
. - C G--~ . (VIII), )~ / \ \ ~
/ .=. O
(R)m R ~ ~R (R')m, which is then condensed with an alkali metal salt of an imidazole or 1,3,4-triazole, in an inert organic solvent, to give a compound of formula III.

In the formulae (V), (VI), (VII) and (VIII) above, R, m, m', R, R', Rl, R2 and R5 are as defined for formula I and Hal is a halogen atom, preferably a chlorine or bromine atom.

A compound of formula IV can also be converted, in one or two steps, into the ether of formula I by reaction with 1 mole of each of a compound of the formula R3-X and R4-X
or with 2 moles of one of these compounds, wherein X is a customary leaving group such as a halogen atom, preferably a chlorine or bromine atom, a sulfonyloxy group, an isourea group or an acyloxy group, in an inert organic solvent and in the presence of a base as acid acceptor.

A radical R3 can also be attached, for example as halide, direct to the hydroxyl group of the formula III to give an ether in accordance with the reaction scheme~

' :

:, :

:: , ~: . : :
' :' , ~123p~3~

-~ OH O ~ c OR O o-~
// ~ I 11 R \\ ~ 1 3 11 ~Y ~
C--~ 3 C--C-~
~ / I G=~ base (R)m Rl-C-R2 (R') (R)m Rl-C-R2 (R~)m N N
/\ /\
E O
Il 11 11 11 ~ -N (III) ~---N ~IIIa) The compound of formula IIIa is then further reacted by treatment with a complex metal hydride, a lithium alkyl compound LiR5 or with a magnesium halide R5MgHal, to give a compound of formula I in which R4 is hydrogen and which can subsequently be reacted with 1 mole of a compound of the formula R4-X, in an inert organic solvent and in the presence of a base, to give an ether of the formula I.

A compound of formula Ic can be condensed with an aldehyde or a \ /
ketone of the formula O=C-R6 or the ketal thereof R6-C-R7 to give a glycol ether of formula Ie \ /
C
--- O 0 6~
// ~ I I // ~
a ~--C---G-- ~ (Ie), )t / I I \ X~
~ 5 (R)m Rl--G-R2 (R') N
E o Il 11 .
~---N

: ' . ~ , 3~

wherein E, m, m', R, R', Rl, R~, R5, R6 and R7 are as defined for formula I and R8 is Cl-C6alkyl.

The process of this invention comprises reducing a compound of formula III
-- OH O ~--// \\ I 11 // \\
~ G---rr~
)~ / 1 1, \ )~, ~ R5 o=- \
(R)m Rl-C-R2 (R')m, N
E O
Il 11 _---N

wherein E, m, m', R, Rl and R2 are as defined for formula I, with a complex metal hydride or with hydrogen and a catalyst, with a lithium alkyl compound LiR5 or with a magnesium halide R5MgHal, in an inert organic sol~ent, and reacting the resultant diol of formula Ic as described above.

Compo.unds of formula Id, in which Rl, R2 and R3 are hydrogen and R~
is Cl-C4alkyl, can also be prepared by alkylating a substituted benzoin of formula IX
-- O OH ---// \\ 11 1 // \\
~ CH- o (IX), X / \ ~
(R) (R') , m m : wherein m, m', R and R' are as defined for formula I, with acompound of formula R'4-X, wherein R'4 is a Cl-C4alkyl group and X
is a leaving group, for example a halogen atom or a sulfonyloxy, isourea or acyloxy group, in an inert organic solvent and in the . . .

:.. :
,~ , : ................ . .
~ "

:~3~363S~

presence oE an equimolar amount of a base such as sodium hydride, then epoxidising the keto group with dimethylsulfoxonium methylide to give the epoxide of formula X
o-- OR' --

4//
---CH- (X), ~ / \ \ )( / 0=- O '=- \

(R)m ( 'Ç2 (R')m' wherein m, m', R and R' are as defined for formula I and R'4 is a Cl-C4alkyl group, and subsequently opening the epoxide ring with an imidazole or 1,2,4-triazole in the presence of a base.

A further method of preparing diazolyl- or triazolyl-2,3-diphenyl-propane-2,3-diols of formula Ib comprises hydroxymethylating the benzoin of formula IX with formaldehyde, in the presence of a base, in accordance with the reaction scheme -- OH O ~ OH O ~-~
11 // \\ CH2 // ~ I 11 //
~-CH----S-~ > -G---C-o ~ base / O--~ I 0 =~ \
(R)m (R') , (R)m CH20H (Rl)m (IX) (XI) and esterifying the resultant 2,3-diphenyl~1,2-hydroxy-3-oxopropane of formula IX at the primary alcohol radical to give a reactive ester, for example with methanesulfonyl chloride, then reacting said ester with an imidazole or 1,2,4-triazole, in the presence of a base, and, finally, reducing the keto group of the resultant compound of formula XII

~ .

~- , .

:~Z38~3~

.-o OH O ~-// \\ I 11 ~ \\
~ - - C- - - { - - 9 (XII), /)~.=0/ I \~
(R) CH (R') , m 1 2 m N
E
Il 11 N

for example with a complex hydride or with hydrogen in the presence of a catalyst.

In the formulae above, E, m, m', R and R' are as defined for formula I.

The reactions may be carried out in the presence of a base as acid acceptor or of a condensing agent. Examples of suitable bases are organic and inorganic bases such as secondary or tertiary amines (diethylamine, triethylamine, dipropylamine and tripropylamine), pyridine and pyridine bases (4-dimethylaminopyridine, 4-pyrrolidyl-aminopyridine), and oxides, hydrides, hydroxides, carbonates and bi-carbonates of alkali metals and alkaline earth metals. Further suitable bases are alkali metal acetates and alkali metal alco-holates.

It can also be advantageous to use the 1,2,4-triazole or imidazole in the form of an alkali metal salt by reacting it first, for example, in situ with an alkali metal alcoholate.
....

It is preferred to use N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, acetonitrile and benzonitrile as inert organic solvents. These solvents are used alone or in combination with other inert solvents such as benzene, toluene, xylene, hexane, petroleum ether, chlorobenzene or nitrobenzene.

.

"

8~39`

The condensation reactions are carried out in the temperature range from -10C to the boiling point of the solvent.

The reaction of the ~-haloketone of ormula II with paraformaldehyde or a ketone 0=C-Rl is conducted in the presence of a strong non-nucleophilic base such as an alkali metal hydride (NaU), with subsequent addition of the imidazole or l,2,4-triazole or, preferab-ly, of an alkali metal salt thereof. The reaction is carried out in the temperature range from 0 to about 140C, preferably from lO to 80C, and in an anhydrous solvent such as N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, hexamethylphosphoric triamide, N-methylpyrrolidone, acetonitrile, ether, tetrahydrofuran or dioxan.

The starting materials of formula II are known or they can be prepared in known manner, for exanple by chlorinating benzoins of formula IX.

The deoxybenzoins of formula VI are known or can be prepared by a Friedels-Craft reaction from a phenylacetyl halide and a benzene, in accordance with the scheme:

--o ~) e ~
-CH C-Hal ~ o --3 ~ -CH C0-~ ~VI) 2 ~ ~ ~ / 2 O = ~ \
~ (R) (R )m~ (R)m (R~;)m :
The compounds of formula VI can likewise be obtained by condensing a ; benzoic acid ester with a benzyl nitrile, subsequently hydrolysing the cyano group, and decarboxylating the carboxyl ester so obtained, in accordance wLth the s~heme:

: ' ';

, ,~ . ' ~ ' ~ ' ~LZ~ 391 _ _"
// ~ // ~
-COOalkyl + NCCH2-- o ->
)~ / \ )~
=0 .=0 \
(R)m (R') ._- O CN ~~
// ~ 11 1 // ~ hydrolysis ~-G-CH2- ~ - 3 + decarboxylation - 3 VI
)~ / \ )~ H2S4/H2 ~ = O
(R)m (R') , m The compounds of formula VI can also be prepared for example by a Grignard reaction from a benzoic acid salt, preferably the lithium sale, and a benzyl magnesium halide, in accordance with the scheme:

--- O ~_~
R \\ 11 // ~
~-C-O Salz ~ Hal Mg CH
~ / 2 (R)m (R')m, ~--o O
// ~ 11 // ~
-c-cH2-~ ~ (YI) )~ / \ )( (R) (R'~ , m m Hydrogenation and reduction reactions are carried out in anhydrous inert solvents such as ether, dioxan, tetrahydrofuran, benzene, toluene, xylene and the like. As reducing agent, the complex metal hydride such as lithium aluminium hydride, sodium borohydride~ an alkali metal hydride or also hydrogen, can be used with a catalyst, for example palladium or platinum on carbon. If it is desired to introduce an alkyi radical R5 it is advisable to use a magnesium halide R5MgHal or a lithlum, potas6ium or sodium compound of R5.

, ~3~3~ 21489-66~5 The l-diazolyl- and l-triazolyl-2,3-diphenylpropane ccmpounds of formula I contain asyrnmetrical carbon AtomS in positions 2 and 3, and they can be obtained as enantiomers and dia~tereoisomers which can be resolved in conventional manner into the pure optical antipodes, for example by fr&ctional crystallisation of salts with optically strong acids or bases. Diastereoisomers can be separated for example by column chromatography an~ then resolved into the enantiomers.

The enantiomers can have different biological properties and there may be a graduated difference in activity while the activity spectrum remains the same. The present invention relates to all pure stereoisomers, enantiomer~ and to the mixtures thereof in which the compounds of formul~ I may be obtained.

The above described preparatory process, including all partial steps, constitutes an important object of the present invention.

Surprisingly, it has now been found that the novel compound~ of formula I and compositions containing them are characterised in particular by their selective in~luence on plant metabolism. Thi-~selective influence on the physiological procesaes of plant develop-ment makes it possible to use the compounds of formula I for different purposes, especially for those in connection with in-- creasing the yield of useful plants, with facilitating harvesting, and with labour-~aving in measures taken in crop~ of cultivated plants.

Previous experience with growth regulators hAs shown that they are able to induce one or more different responses in the plants to which they are applied. These different responses depend substan-tially on the time of application, based on the developmental sta~e of the seed or of the plant, the nature of the application, as well as on the concentrations of active ingredient ~pplied to the plants ~7~
. . .

123~3g or to the locus thereof. Growth regulators should at all events induce positive responses in the cultivated plants in the desired manner.

Growth regulators may be used e.g. for inhibiting vegetative plant growth. Such a growth inhibition is of economic interest, inter alia, in respect of grasses, as the frequency of cutting in flower gardens, parks, sports fields or road shoulders can thereby be reduced. Of importance too is the inhibition of growth of herbaceous and ligneous plants on road shoulders and near transmission lines, or generally in areas in which strong growth is undesirable.

The use of growth regulators for inhibiting the growth in height of cerealg iB also important, as shortening the stalks diminishes or completely eliminates the danger of lodging before harvesting. In addition, growth regulators are able to bring about a strengthening of the stalks in crops of cereals, whereby lodging is also counter-acted.
Inhibition of the vegetative growth of many cultivated plants permits more plants to be sown in a crop area, so that a higher yield may be obtained per unit of area. A further mechanism of yield increase using growth regulators resides in the fact that nutrients are able increasingly to promote flower formation and fruiting, whereas vegetative growth is inhibited.

Growth regulators are also frequently able to promote vegetative growth. This iB very beneficial when the vegetative parts of plants are to be harvested. However, promotion of vegetative growth can also result simultaneously in promotion of generative growth, so that e.g. more or larger fruit is formed.

Yield increases may also often be obtained by influencing the plant metabolism, for example by increasing photosynthetic efficiency, without any visible changes in vegetative growth. Growth regulators can also induce a change in the composition of plants, so that the quality of the harvest produce is improved. For example, it is , . .

.. .

~3~3S~9 possible to increase the sugar content of sugar beet, sugar cane, pineapples and citrus fruit, or to increase the protein content of soya beans or cereals.

The use of growth regulators can lead to the formation of partheno-carpic fruit. The sex of blossoms can also be influenced. The production or flow of secondary plant substances can also be positively influenced by growth regulators, for example the stimu-lation of the flow of latex in rubber trees.

During plant growth, the development oE side-shoots can also be pro-oted by the chemical interruption of apical dominance using growth regulators. This is of interest e.g. in the propagation of plant cuttings. However, it is also possible to inhibit the growth of side-shoots, e.g. in tobacco plants after decapitation in order to prevent the formation of side-shoots, and thus to promote leaf growth.

Premature fruit drop can be prevented by the use of growth regula-Cors. However, it is also possible to promote fruit drop to a specific extent, e.g. in fruit crops, by means of chemical thinning.
~rowth regulators can also be used for reducing the force necessary for detaching fruit at harvesting, so making possible mechanical harvesting of plants or facilitating manual harvesting.

With growth regulators it is also possible to speed up or delay the ripening of harvest products before or after harvesting. This is particularly advantageous, because a best possible accommodation to market requirements can thereby be achieved. In addition, growth regulators can often improve the colour of fruit. With the aid of growth regulators it is also possible to concentrate ripening at a particular time. The conditions are thus created for a complete mechanical harvesting of e.g. tobacco, tomatoes or coffee, or for manual harvesting, in only one single operation.

_.

:. ~ . ;;:, ~2~;39 The application of growth regulators can also make it possible to influence the dormancy of seeds and buds of plants, i.e. the endogenic annual rhythm, so that plants, e.g. pineapples, or ornamentals in nurseries, germinate, sprout or blossom at a time when they would normally not tend to do so.

With growth regulators it is also possible to delay budding or the germination of seeds, e.g. in order to avoid damage by late frosts in areas endangered thereby. Conversely, root growth and/or the formation of shoots can be stimulated, so that growth may be restricted to a shorter period.

Growth regulators can also impart halophilic properties to culti-vated plants. The conditions are thus created for cultivating plants in salty soil. Growth regulators can also induce resistance to frost and drought in plants.

Under the influence of growth regulators, the ageing (senescence) of p]ants or parts of plants can be inhibited or delayed. Such a response can be of great economic importance, as the storability of treated parts of plants or whole plants such as fruit, berries, vegetables, salads or ornamentals can be improved or prolonged after harvesting. Likewise, a substantial yield increase can be obtained by treating cultivated plants by prolonging the phase of photo-synthetic activity.

A further improtant field of use for growth regulators is the inhibition of excessive growth of tropical cover crops. In tropical and subtropical monocultures, e.g. in palm tree plantations, cotton and maize fields etc., cover crops, especially species of legu-minosae, are often planted with the objected of maintaining or improving the quality of the soil (prevention of desiccation, supplying nitrogen) and of preventing erosion. By applying the compounds of this invention it is possible to control the growth of :, : ' ' ' 238635~

these cover crops and so to keep the growth in height of these plants at a low level, thereby ensuring healthy growth of the culti-vated plants and the maintenance of favourable soil conditions.

Target crops to be protected within the scope of the present invention comprise e.g. the following species of plants:
cereals (wheat, barley, rye, oats, rice, sorghum and related crops), beet (sugar beet and fodder beet), drupes, pomes and soft fruit (apples, pears, plums, peaches, almonds, cherries, strawberries, rasberries and blackberries), leguminous plants (beans, lentils, peas, soybeans), oil plants (rape, mustard, poppy, olives, sun-flowers, coconuts, castor oil plants, cocoa beans, groundnuts), cucumber plants (cucumber, marrows, melons) fibre plants (cotton, flax, hemp, jute), citrus fruit (oranges, lemons, grapefruit, mandarins), vegetables (spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, paprika), lauraceae (avocados, cinnamon, camphor), or plants such as maize, tobacco, nuts, coffee, sugar cane, tea, vines, hops, bananas and natural rubber plants, as well as ornamentals (composites), areas of grass, embankments or general low cover crops which counteract erosion or desiccation of the soil, and are useful in cultures of frees and perennials (fruit plantations, hop plantations, maize fields, vineyards etc.) The compounds of formula I also have herbicidal properties. At high rates of application they can be used as total herbicides for maintaining traffic routes, sites, sports facilities, canalisations and the like free from plant growth. At low rates of application they are suitable for selective weed control in large-scale crops of useful plants, for example cereals, maize, sorghum, rice, soybeans, cotton, rape, sunflowers, poppies etc.
-The compounds of formula I are normally applied in the form ofcompositions and can be applied to the crop area or plant to be treated, simultaneously or in succession, with further compounds.
These further compounds can be both fertilisers or micronutrient donors or other preparations that influence plant growth. They can ~: :
. . . :
'`
i:
: , . ~

. ' ,:
. ~
,. , also be selective herbicides, insecticides, fungicides, bacterici-des, nematicides, mollusicides or mixtures of several of these preparations, if desired together with further carriers, surfactants or application promoting adjuvants customarily employed in the art of formulation. Suitable carriers and adjuvants can be solid or liquid and correspond to the substances ordinarily employed in formulation technology, e.g. natural or regenerated mineral sub-stances, solvents, dispersants, wetting agents, tackifiers, thick-eners binders or fertilisers.

A preferred method of applying a compound of the formula I or an agrochemical composition which contains at least one of said compounds, is foliar application. The number of applications and the rate of application depend on the risk of infestation by the corresponding pathogen (type of fungus). ~owever, the compound of formula I can also penetrate the plant through the roots via the soil (systemic action) by drenching the locus of the plant with a liquid composition, or by applying the compounds in solid form to the soil, e.g. in granular form (soil application). The com?ounds of formula I may also be applied to seeds (coating) by impregnating the seeds either with a liquid formulation containing a compound of the formula I, or coating them with a solid formulation. In special cases, further types of application are also possible, e.g. selec-tive treatment of the plant stems or buds.

The compounds of the formula I are used in unmodified form or, preferably, together with the adjuvants conventionally employed in the art of formulation, and are therefore formulated in known manner to emulsifiable concentrates, coatable pastes, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granulates, and also encapsulations in e.g. polymer substances. As with the nature of the compositions, the methods of application, such as spraying, atomising, dusting, scattering or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances. Advantageous rates of application are .

.
~.

~2~8e;3~

normally from 50 g to 5 kg of active ingredient (a.i.) per hectare, preferably from 100 g to 2 kg a.i./ha, most preferably from 200 g to 600 g a.i./ha.

The formulations, i.e. the compositions or preparations containing the compound (active ingredient) of the formula I and, where appropriate, a solid or liquid adjuvant, are prepared in known manner, e.g. by homogeneously mixing and/or grinding the active ingredients with extenders, e.g. solvents, solid carriers and, where appropriate, surface-active compounds (surfactants).

Suitable solvents are: aromatic hydrocarbons, preferably the fractions containing 8 to 12 carbon atoms, e.g. xylene mixtures or substituted naphthalenes, phthalates such as dibutyl phthalate or dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols and glycols and their ethers and esters, such as ethanol, ethylene glycol monomethyl or monoethyl ether, ketones such as cyclohexanone, strongly polar solvents such as N-methyl-2-pyrro-lidone, dimethylsulfoxide or dimethylformamide, as well as vegetable oils or epoxidised vegetable oils such as epoxidised coconut oil or soybean oil; or water.

The solid carriers used e.g. for dusts and dispersible powders, are normally natural mineral fillers such as calcite, talcum, kaolin, montmorillonite or attapulgite. In order to improve the physical properties it is also possible to add highly dispersed silicic acid or highly dispersed absorbent polymers~ Suitable granulated adsorp-tive carriers are porous types, for example pumice, broken brick, sepiolite or bentonite; and suitable nonsorbent carriers are materials such as calcite or sand. In addition, a great number of pregranulated materials of inorganic or organic nature can be used, e.g. especlally dolomite or pulverised plant residues.

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Depending on the nature of the compound of the formula I to be formulated, suitable surface-active compounds are nonionic, cationic and/or anionic sufactants having good emulsifying, dispersing and wetting properties. The term "surfactants" will also be understood as comprising mixtures of surfactants.

Suitable anionic surfactants can be both water-soluble soaps and water-soluble synthetic surface-active compounds.

Suitable soaps are the alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts of higher fatty acids (C10-C22), e.g. the sodium or potassium salts of oleic or stearic acid, or of natural fatty acid mixtures which can be obtained e.g. from coconut oil or tallow oil. Mention may also be made of fatty acid methyltaurin salts.

More frequently, however, so-called synthetic surfactants are used, especially fatty sulfonates, fatty sulfates, sulfonated benzimid-azole derivatives or alkylarylsulfonates.

The fatty sulfonates or sulfates are usually in the form of alkàli metal salts, alkaline earth metal salts or unsubstituted or sub-stituted ammonium salts and contain a C8-C22alkyl radical which also includes the alkyl moiety of acyl radicals, e.g. the sodium or calcium salt of lignosulfonic acid, of dodecylsulfate or of a mixture of fatty alcohol sulfates obtained from natural fatty acids.
These compounds also comprise the salts of sulfuric acid esters and sulfonic acids of fatty alcohol/ethylene oxide adducts. The sulfona-ted benzimidazole derivatives preferably contain 2 sulfonic acid groups and one fat~y acid radical containing 8 to 22 carbon atoms.
Examples of alkylarylsulfonates are the sodium, calcium or tri~
ethanolamine salts of dodecylbenzenesulfonic acid, dibutylnaphtha-:

1:Z3~3S3~

lenesulfonic acid, or of a naphthalenesulfonic acid/formaldehyde condensation product. Also suitable are corresponding phosphates, e.g. salts of the phosphoric acid ester of an adduct of p-nonyl-phenol with 4 to 14 moles of ethylene oxide.

Non-ionic surfactants are preferably polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, or saturated or unsaturated fatty acids and alkylphenols, said derivatives containing 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon moiety and 6 to 18 carbon atoms in the alkyl moiety of the alkylphenols.

Further suitable non-ionic surfactants are the water-soluble adducts of polyethylene oxide with polypropylene glycol, ethylenediamine propylene glycol and alkylpolypropylene glycol containing 1 to lO
carbon atoms in the alkyl chain, which adducts contain 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups. These compounds usually contain l to 5 ethylene glycol units per propylene glycol unit.

Representative examples of non-ionic surfactants are nonylphenol-polyethoxyethanols, castor oil polyglycol ethers, polypropylene/
polyethylene oxide adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxyethoxyethanol. Fatty acid esters of polyoxyethylene sorbitan and polyoxyethylene sorbitan trioleate are also suitable non-ionic surfactants.

Cationic surfactants are preferably quaternary ammonium salts which contain, as N-substituent, at least one C8-C22alkyl radical and, as further substituents, unsubstituted or halogenated lower alkyl, ben~yl or lower hydroxyalkyl radicals. The salts are preferably in the form of halides, methylsulfates or ethylsulfates, e.g. stearyl-trimethylammonium chloride or benzyldi(2-chloroethyl)ethylammonium bromide.

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The surfactants customarily employed in the art oP formulation are described e.g. in "McCutcheon's Detergents and Emulsifiers Annual", MC Publishing Corp. Ringwood, New Jersey, 1979; Helmut Stache, "Tensid-Taschenbuch", Carl Hanser Verlag, Munich/Vienna, 1981.
J. and M. Ash, "Encyclopedia of Surfactants", Col. I-III, Chemical Publishing Co. Inc., New York, 180-81.

The agrochemical compositions usually contain 0.1 to 99 ~, prefer-ably 0.1 to 95 ~, of a compound of the formula I, 1 to 99 ~ of a solid or liquid adjuvant, and 0 to 25 ~, preferably 0.1 to 25 ~, of a surfactant.

Whereas commercial products are preferably formulated as concen-trates, the end user will normally employ dilute formulations.

The compositions may also contain further ingredients such as stabilisers, antifoams, viscosity regulators, binders, tackifiers as well as fertilisers or other active ingredients in order to obtain special effects.

The invention is illustrated in more detail by the following Examples, without implying any restriction to what is described therein. Parts and percentages are by weight.

, .

~!L2~8~39 Example 1: Preparation of 2-(2,4-dichlorophenyl)-1-phenyl-3-(1,2,4-triazol-l-yl)propane-1,2-diol Cl I

-- OH OH -^
// ~ I I // ~
Cl-~ C Cl~-o \ / I I \ /
=o I R5 .=.
l H2 N
N
Il 11 . N

45 g of 1-benzoyl-1-(2,4-dichlorophenyl)-2-(lH-1,2,4-triazol-1-yl)-ethanol are dissolved in ~00 ml of methanol and then, with stirring, 7.4 g of sodium borohydride (NaBH4) are added in portions while cooling to 5-10C. Stirring is continued for 15 hours at room temperature and then 50 ml of concentrated hydrochloric acid are stirred in dropwise under nitrogen. The reaction mixture is stirred for a further 5 hours at room temperature and then concentrated by evaporation. The residue is taken up in about lOO ml of methanol the solution is concentrated by evaporation. The residue is made strongly alkaline with 10~ aqueous sodium hydroxide solution (pH 12) and extracted with methylene chloride. The organic phase is washed with water, dried over sodium sulfate and concentrated by evaporat-ion~ The residue is recrystallised from tetrahydrofuran/hexane, affording white crystals of the title compound with a melting point of 187-189C.

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The following compounds are prepared in analogous manner:
OH OH -~
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(R~m ICH2 (R~) N
E
Il 11 . N

Table 1:

No, : - ' = (R~)m~ ~Physlcal data (C) 1 Ol N 2~4-C12 - m.p. 187-189 1.03 N 4-Cl _ m.p. 147-148~
1.04 N 4-Cl 4-Cl m.p. 168-170 1.05 N 4-Cl 2-Cl m.p. 180-181 L.06 N 4~Cl 2,4-Cl 1.07 N 4-F 4-Cl m.p. 153-154 1.08 N 4-CF3 _ 1.09 N 4-CF3 4-Cl m.p. 148-150 1.10 N 4-CF3 2,6-Cl l.il N 4-CF3 2,4-Cl 1.12 N 4-CF3 4-CH3 1.13 N 4-Br 4-Cl m.p. 178-180 1.14 N 4-Br _ m.p. 140-141 1.15 N 4-Br 2-Cl _ ' . '` ~ .

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Tabl_ 1: (Continuation) ~ __ .
No. E (R)m (R~)m, Physical data (DC) 1.16 N 4-Br 2,4-C12 1.17 N 2-Br 4-CH3 1.18 N 3-CF3 _ 1.19 N 3-CF3 4-Cl m.p. 148-150 1.20 N 3-CF3 3-CF3 1.21 N 3-CF3 4-CH3 1.22 N 3-CF3 2,3-C12 1.23 N 2-F _ 1.24 N 2-Cl _ m.p. 176-174 1.25 N 2-Cl 4-Cl m.p. 172-174 1.26 N 4-OC6H4Cl _ 1.27 N 2,4-C12 2,4-(CH3)2 dia91:ereoisomerA
diastereoisomer B
m.p. 188-191 1.28 N 4-F 4-F
1.29 N 3-F 4-F
1.30 N 4-Cl 4-Br m.p. 60-62 1.31 N 4-Cl 3-CF
1.32 N 4-Cl 4-F m.p. 163-164 1.33 N 4-Cl 4-CH3 m.p. 169-170 1.34 N 4-Cl ~ 4-OCH3 m.p. 147-19 ~
1.35 N 4-Cl ~ 4-CF3 m.p. 185-187 1.36 N 4-Cl 3,4-Cl m.p. 170-172 1.37 N 4-Cl 2-F m.p. 164-166 :::: : : ~ ~:

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:~2~ 39 Table 1: (Continuation) NoO E (R)m (R')m, Physical data ('C) _, .
1.38 N 4-Cl 2-CH3 m.p. 136-138 1.39 N 4-Cl 2-CH3 m.p. 149-150 1.40 N 4-Cl 2,5-Cl 1.41 N 4-F _ m.p. 188-189 1,42 N 4-Cl 2-OCH3 2,6-C12 1.43 N 4-CH3 m.p. 135-136 1.44 N 4-CH3 2-Cl 1.45 N 4-CH3 4-Cl 1.46 N _ 2-Cl 1.47 N _ 3-Cl m.p. 14-150 1.48 N _ 4-C1 m.p. 145-146 1.49 N _ 4-OCH3 l.SO N 3-Cl _ m.p. 13S-137 1.51 N 3-Cl 4-Cl m.p. 123-125 1.52 N _ 2,4-Cl 1.53 N _ 4-F
1.54 N _ 2-F
1.55 N 2,4-C12 2,4-C12 m.p. 109-113 1.56 N 2,4-C12 2-Cl, 4-CH3 1.57 N 2,4-C12 4-CH3 m.p. 176-180 1.58 N 2,4-C12 4-C1 m.p. 178-179 1.59 N 2,4-C12 4-OCH3 1.60 N 2,4-C12 2-Cl _ : .; ' . :' '' ' . : ~,.

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Table 1: (Continuation) No~ _ _ ~ (R') , Physica, data (C) 1.61 N 2,4-C12 4-F
1.62 N 2,4-G12 2-F
1.63 CH 2 4-Cl _ 1.64 CH _ _ 1.65 CH 4-Cl _ 1.66 CH 4-Cl 4-Cl 1.67 CH 4-Cl 2-Cl 1.68 CH 4-Cl 2,4-C12 1.69 CH 4-F 4-Cl 1.70 CH 4-CF3 _ 1.71 CH 4-CF3 4-Cl 1.72 CH 4-CF3 2,6-Cl 1.73 CH 4-CF3 2,4-C12 1.74 CH 4-CF3 4-CH3 1.75 CH 4-Br 4-Cl 1.76 CH 4-Br _ 1.77 CH 4-Br 2-Cl ~ :
1.78 CH 4-Br 2,4-CI
1.79 CH 2-Br 1.80 CH 3-CF3 1.81 CH 3-CF3 4-CI
1.82 CH 3-CF3 3-CF3 1.83 CU ~ _ . _ __ , ' ,.

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lZ38639 Table 1: (Continuation) _ . . _ No. E (R)m (Rl)m, Physical data (C) 1.84 CH 3-CF3 2,3-C12 1.85 CH 2-F _ 1.86 CH 2-Cl _ 1.87 CH 2-Cl _ 1.88 CH 6 4 _ 1.89 CH 2~4-C12 2,4 (CH3)2 1.90 CH 4-F 4-F

1.93 CH 4-Cl 3-CF3 .

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~2381i,39 ~-o OR OR o-o ~ 3 1 4 //
s--C CH--~ o ~ / I I \ ~
~ Rs =o \
(R)m fH2 (R')m' N

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E
Il 11 Table 2:
No. E (R)m 3 4 R5 ~R')m, Physical 2.01 N 2,4 C12 CH3 H CH3 _ 2.02 N 2,4 C12 -C(CH3)2- H _ m.p. 162-165 2.03 N 2,4 C12 -C(C2H5)2- H 2,4 C12 2.04 N 4-Cl CH3 H C3H7n 2.05 N 4-Cl CH3 H C3H7i _ 2.06 N 4-Cl CH3 H CH3 2.07 N 4-Cl CH2CH=CH2 H _ 2.08 N 4-Cl -C(CH3)2- H 4-CI
2.09 N 4-Cl ~C(CH3)2- H 4-Br ; 2.10 N 4-Cl -C(CH3)2- U 3-CF3 :: : : ::
:

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Table 2: (Continuation) No. E (R) R3 R4 R5 (R') daYa (C) . ..
2.11 N 4-Cl -C(CH3)2- H 4-CH3 2.12 N 4-Cl -C(CH3)2- H 4-F
2.13 N 4-F -C(CH3)2- H 4-F
2.14 N 3-F -C(CH3)2~ H 3-F
2.15 CH2,4 C12 CH3 H CH3 _ 2.16 CH2,4 C12 -C(CH3)2- H _ 2.17 CH2,4 C12 -C(CH3)2- H 2,4 C12 2.18 CH 4-C1 CH3 H C3H7n _ 2.19 CH 4-Cl CH3 H C3H7i _ 2.20 CH 4-Cl CH3 H CH3 _ 2.21 CH 4-Cl CH2CH=CH2 H H _ 2.22 CH 4-Cl -C(5H3)2- H 4-Cl 2.23 CH 4-Cl -C(CH3~2- H 4-Br 2.24 CH 4-Cl -C(CH3)2- H 3-CF3 2.25 CH 4-Cl -C(CH3~2- H 4-CH3 2.26 CH 4-Cl -C(CH3)2- H 4-CH3 2.27 CH 4-Cl -C~CH3)2- H 4-F
2.28 CH 4-F -C(CH3)2 H 4-F
2.29 CH 3-F 3 CH3 3-F
2.30 N 2,4 C12 -C(CH3)2- H _ 2.31 N 2,4 C12 -C(CH3)2- H 2 4-Cl 2.32 N 2,4 C1~ -C(CH3)2- H 4-C1 m.p. 183-185 2.33 N 2,4 C12 CH3 CH3 H 4-CH3 m.p. 5S-57 2.34 N 2,4 C12 C2H5 C2H5 H 4-Cl m.p. 65-102 2.35 N 2,4 C12 3 H 2,4-C12 2.36 N 2,4 C12 C2H5 H H 294-C1 m.p. 59-68 ::
_ . _ _ _~ _ _ _ _:

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, ~3~639 21489~6645 Table 2: (Continuation) No. E (R)m R3 R4- R5 - ~R )m~
..
2.37 CH 4-Cl -C(CH332- H 4-F
2.38 CH 4-F -C(CH3)2- H 4-F
2.39 CH 3-F -C(CH3)2- H 3-F
2.40 CH 2,4-C12 CH3- H CH3 _ 2.41 N 2,4-Cl -C(CH3)2- H 2,4-di-Cl 2.42 N 2,4-C12 ( 3)2 H 4-Cl 2.43 N 2,4-C12 -C(CH3)2- H 4-CH3 2.44 N 2,4-C12 CH3 CH3 H 4-Cl 2.45 N 2~4-CI2.. _ 2 5 2 5 H 2,4-di-Cl ' `

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-~ OH OH o-~
// ~ I I // ~
. .- G- - G-- . (Ib), )~ / I I \ )( / ~=o I Rs (R)m R1-C-Rz (R') , N

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Table 3:

50. E ~R) Rl R2 R5 (R~m~

3.01 N 2,4 C12 C2H5 H H
3.02 N 2,4 C12 c3H7n H H _ 3.03 N 4-Cl C2H5 H H _ 3.04 N 4-Cl CH3 H H 4-Cl 3.05 N 4-Cl C2H5 H H
3.06 CH 2,4 C12 C2H5 H H
3.07 CH 2,4 C12 c3H7n H H
3.08 CH 4-Cl C2H5 H U
3.09 CH 4-CI CU3 H H 4-Cl 3.10 CH 4-Cl C2H5 H U 4-Cl :

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~23~39 Formulation Examples The compounds of formula I will not normally be used by themselves in agriculture. They are used in the form of ready for use formulat-ions which can be used either direct or diluted with water.

Example 2:
Dusts: The following substances are used to formulate a) a 5~ and b) a 2~ dust:

a) 5 parts of compound of formula I
parts of talcu~;
b) 2 parts of the above compound or of a mixture 1 part of highly dispersed silicic acid 97 parts of talc;

The active ingredients are mixed with the carriers and ground and in this form can be processed to dusts for application.

~xample 3:
Granulate: The following substances are used to formulate a 5 granulate:

parts of compound of formula I
0.25 part of epoxidised vegetable oil 0.25 part of cetyl polyglycol ether 3.25 parts of polyethylene glycol 91 parts of kaolin (particle size 0.3 - 0.8 mm).

The active ingredient or mixture is mixed with the vegetable oil and the mixture is dissolved in 6 parts of acetone. Then polyethylene glycol and cetyl polyglycol ether are added. The resultant solution :
:

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is sprayed on kaolin and the acetone is evaporatecl in vacuo. A
microgranular formulation of this kind can be conveniently in-corporated in seed furrows.

Example 4_ Wettable powders: The following constituents are used to formulate a) a 70 ~, b) a 40 ~, c) and d) a 25 ~ and e) a 10 ~ wettable powder:

a) 70 parts of compound of formula I
parts of sodium dibutylnaphthylsulfonate 3 parts of naphthalenesulfonic acid/phenolsulfonic acid/
formaldehyde condensate (3:2:1) parts of kaolin 12 parts of Champagne chalk b) 40 parts of active ingredient parts of sodium lignosulfonate 1 part of sodium dibutylnaphthalenesulfonate 54 parts of silicic acid c) 25 parts of active ingredient 4.5 parts of calcium lignosulfonate 1.9 parts of Champagne chalk/hydroxyethyl cellulose mixture (1:1) 1.5 parts of sodium dibutylnaphthalenesulfonate 19.5 parts of silicic acid 19.5 parts of Champagne chalk 28.1 parts of kaolin d) 25 parts of active ingredient 2.5 parts of isooctylphenoxy polyoxyethylene ethanol 1.7 parts of a Champagne chalk/hydroxyethyl cellulose mixture (1:1) 8.3 parts of sodium aluminium silicate 16.5 parts of kieselguhr . .

, ~

:' 46 parts of kaolin e) 10 parts of active ingredient 3 parts of mixture of the sodium salts of saturated fatty alcohol sulfates parts of naphthalenesulfonic acid/formaldehyde condensate 82 parts of kaolin.

The active ingredients are intimately mixed in suitable mixers with the additives and ground in appropriate mills and rollers. Wettable powders of excellent wettability and suspsension power are obtained.
These wettable powders can be diluted with water to give suspensions of the desired concentration and can be used in particular for foliar application (to inhibit growth or for fungicidal applica-tion).

Example 5:
Emulsifiable concentrate: The following substances are used to -formulate a 25 ~ emulsifiable concentrate:

parts of active ingredient 2.5 parts of epoxidised vegetable oil parts of an alkylarylsulfonate/fatty alcohol polyglycol ether mixture parts of dimethyl formamide 57.5 parts of xylene.

Exa~.ple 6:
Paste The following substances are used to formulate a 45 ~ paste:

a) 45 parts of active ingredient parts of sodium aluminium silicate, 14 parts of cetyl polyglycol ether with 8 moles of ethylene oxide, 3 parts of oleyl polyglycol ether with 5 moles of ethylene oxide, ~ ~ :

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~L%~8639 2 parts of spindle oil, parts of polyethylene glycol~
23 parts of water.

b) 45 parts of the above active ingredient or mixture, parts of ethylene glycol, 3 parts of octylphenoxy polyethylene glycol containing 9-10 moles of ethylene oxide per mole of octylphenol, 3 parts of a mixture of aromatic sulfonesulfonic acids, condensed with formaldehyde as ammonium salt, 1 part of silicone oil in form of a 75 ~ emulsion, 0.1 part of a mixture of 1-(3-chloroallyl)-3,5,7-triazo-azonium-adamantane chloride with sodium carbonate (chloride value at least 11.5 ~), 0.2 part of a biopolymeric thickener containing a maximum of 100 bacilli per gram, 42.7 parts of water.

The ative ingredient is intimately mixed with thP adjuvants in appropriate devices and ground. By diluting the resultant paste with water, it is possible to prepare suspensions of the desired concentration.

Biological Examples The herbicidal and plant growth regulating activity was determined in the following tests.

Example 7: Preemergence herbicidal_activity In a ~reenhouse, seeds of plants are sown in flower pots with a diameter of about 11 cm such that 12-25 plants are able to develop in each pot. Directly after sowing, the surface of the soil is treated with an aqueous emulsion of the test compound, which is diluted and sprayed such that it corresponds to a concentration of 4, 2, 1, 1/2 and 1/4 kg of active ingredient per hectare (a.i./ha) in field application. The pots are then kept under optimum condi-" :
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tions for plant growth, i.e. with regular watering at 22-25C and 50-70~ relative humidity. The test is evaluated 3 weeks later in accordance with the following rating:

1 plants have not germinated or are withered 2-3 very severe damage 4-6 average damage 7-8 slight damage 9 no activity - normal growth as untreated controls The results are tabulated below.

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Compound 1 ..... _._ Rate of application 4 2 11/2 114 in kg/ha Plant Avena fatua 1 1 1 7 9 Alopecurus myosuroides 2 2 22 3 Echinochloa crus galli 1 1 11 2 Rottboellia exaltata 1 1 12 2 Cyperus escuientus 2 2 99 9 Abutilon sp 1 1 2 2 3 Xanthium sp 1 1 1 2 2 Chenopodium album 1 1 2 2 2 Ipomoea purpurea 2 2 2 3 6 Sinapis alba 2 2 2 3 4 Calcium aparinetus 2 2 23 3 Viola tricolor 2 2 2 2 2 Beta vulgaris 2 2 2 3 3 Example 8: Postemergence application Various cultivated plants and weeds are grown from seeds in pots in a greenhouse until they have attained the 4- to 6-leaf stage. The plants are then sprayed with aqueous emulsions of the test compound (obtained from a 25 % emulsifiable concentrate) at concentrations of 4 and 2 kg/ha. The treated plants are then kept under optimum conditions of light, regular watering, temperature (22-25C) and humidity (50-70 ~). The test is evaluated 15 days after treatment and the condition of the plants is assessed in accordance with the rating in Example 7. The results are as follows:

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~Z3~3~ 21489~6645 ~ 40 -Compound l Rate of applicatlon 4 _ in kg/ha _ Plant Avsna fatua 5 6 Alopecurus myosuroides 7 7 Echinochloa crus galli 4 4 Rottboellia exaltata ~ 7 Cyperu3 esculentu~ 4 5 Abutilon sp 3 6 Xanthium 8p 5 5 Chenopodium album 3 4 Ipomoea purpurea 4 5 Sinapis alba ~ 4 Galium apanne 5 6 Yiola tricolor 7 7 Beta vulgaris 3 Example 9: Selective postemergence herbicidal action on rice Twenty-five-day-old rice plants are transplanted into large receangular asbestos cement containers in a greenhouse. Seeds of the weeds occurring in rice crops, namely Echinochloa, Scirpus, Monocharia, and Sagittaria, are then BoWn between the rows of rice plants. The containers are well watered and kept at a temperature of about 25C and at high humidity. Twelve days later, when the weeds have emerged and reached the 2-3 leaf stage, the soil in each of the containers i~ covered wich a layer of wa~er to a height of 2.5 cm.
:

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~l~3~363~

The test compound is then applied ;n the form of an emulsifiable concentrate with a pipette between the tows of plants. The emulsi-fiable concentrate is diluted and applied such that it corresponds to a field application rate of 2, 1, 1/2, 1/4 and 1/8 kg/ha respec-tively. The test is evaluated 4 weeks later in accordance with the rating employed in the previous Examples. The results are tabulated below.

Compound 1 Rate of application 2 1 1/2 1/4 1/8 in ~g/ha Plant _ Rice 3 4 4 5 7 Echinochloa crus galli 1 1 1 1 1 Scirpus sp. 1 1 1 1 1 Monocharia vaginalis 1 1 1 1 1 Sagittaria pygmea 2 3 3 4 4 Example 10: Growth inhibition of cereals Summar barley (Hordeum vulgare) and summer rye (Secale) are sown in sterilised soil in pLastic beakers in a greenhouse and watered as required. The cereal shoots are treated about 21 days after sowing with an aqueous spray mixture of a compound of the formula I. The concentration corresponds to 0.3 to 2.5 kg of active ingredient per hectare. Evaluation of the growth of the cereals is made 10 and 21 days after application. A comparison with untreated controls shows that the growth of cereal plants treated with compounds of the formula I is significantly reduced. The compound of Example proved particularly effective and reduced the growth rate to 5-25 %.

363~

- ~2 -Example 11: Growth inhibition of grasses Seeds of the grasses Lolium perenne, Poa pratensis, Festuca ovina, Dactylis glomerate and Cynodon dactylon are sown in plastic dishes filled with an earth/peat/sand mixture (6:3:1), in a greenhouse, and watered as required. The emergent grasses are cut back weekly to a height of 4 cm, and about 50 days after sowing and 1 day after the last cut are sprayed with an aqueous spray mixture of a compound of the formula I. The concentration of test compound corresponds to a rate of application of up to 0.3 to 2.5 kg a.i. per hectare. The growth of the grasses is evaluated 10 and 21 days after application.
The compounds of Tables 1 to 3 effected a marked reduction in new growth. The compound of Example 1 effected a particularly marked growth inhibition and reduced new growth almost completely (growth rate about 10 ~.

Example 12: Growth regulation of soybeans . . .
Soybeans of the "Hark" variety are sown in plastic containers in an earth/peat/sand mixture (6:3:1). The containers are put into a climatic chamber and the plants develop to the 5-6 trefoil leaf stage after about 5 weeks by optimum control of temperature, light, fertiliser addition, and watering. The plants are then sprayed with an aqueous mixture of a compound of the formula I until thoroughly wetted. The rate of application corresponds to 500 ppm of active ingredient. Evaluation is made about 5 weeks after application.
Compared with untreated controls, the compounds of the formula I
markedly increase the number and weight of the harvested siliques on the leading shoot. The compound of Example 1 proved particularly effective and, depending on the test, induced a yield increase of 5 to 12 ~.

Example 13: Growth inhibition of cover crops . .
Test plants of the varieties Centrosema plumieri and Centrosema pubescens are reared from cuttings in plastic pots filled with an earth/turf/sand mixture (1:1:1). After they have grown roots, the plants are transplanted into 9 cm pots and watered as required. For further growth the plants are then kept in a greenhouse at a day ~ . ,.
- .

- ~, .~" ,. -. . .

~2~639 - ~3 -temperature of 27C and a night temperature of 21C. The average light exposure is 14 hours (6000 lux~ snd the humidity is 70 %. The plants are cut back to a height of about 15 cm and sprayed 7 days la~er with a spray mixture of the test compound tcorresponding to a rate of application of 0.3 and 3 kg/a.i./ha respectively). Four weeks after application the growth of the plants i~ compared with that of untrèated control plants which have been cut back. It was found that the compound of Example 1 effected a marked growth inhibition of the cover plant~ and reducedl the growth rate to about 10,%.

Example 14: Inhibition of senescence in cereal plants Summer wheat of the "Svenno" variety i9 ~own in pots with compost soil and reared without special climatic conditions. About 10 days after emergence, 10 to 12 cm primary leaves are cut off and put individually into the test tubes containing 20 ml of suspension of test compound (1.25 to 10 ppm). The test tubes are kept in a climatic room at 23C and 70 ~ relative humidity and irradiated daily for an average of 14 hours (10,000 lux). ~valuation of senescence is made 7 days later by comparing the degree of yellowing wi~h still fresh, green leaves. This test shows that compounds of Example 1 markedly inhibit the senescence of the test plants. They inhibited yellowing of the leaves by more than 80 ~ during the te~t period.

Claims (20)

What is claimed is:

1. A 1-diazolyl- or 1-triazolyl-2,3-diphenylpropane compound of the formula I

(I), wherein E is a nitrogen atom or the methine group -CH=, m and m' are each indapendently of the other 0, 1, 2 or 3, R and R' are each independently of ehe other halogen, C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxy, C1-C4haloalkoxy, nitro, cyano, C1-C4alkylthio, phenyl or phenoxy, each unsubstituted or substi-tuted by R(m), or are C1-C4alkoxycarbonyl, C1-C4haloalkylthio, amino, mono- or di(C1-C4alkyl)amino, R1 and R2 are each independently of the other hydrogen or C1-C4alk-yl, R3 and R4 are each independently of the other hydrogen, C1-C4alkyl, C1-C4alkylcarbonyl or, when taken together, are a methylene bridge -CR6R7-, R5 is hydrogen or C1-C4alkyl, and R6 and R7 are each independently of the other hydrogen or C1-C4alkyl or, together with the carbon atom to which they are attached, are a 3- to 6-membered saturated or unsaturated hydrocarbon ring.

2. A 3-diazolyl- or 3-triazolyl-1,2-diphenylpropane compound according to claim 1 of the formula Ia (Ia), wherein E, m, m', R, R', R3, R4 and R5 are as defined in claim 1.

3. A 1-(1,2,4-triazol-1H-1-yl)-2,3-diphenylpropane-2,3-diol derivative according to claim 1 of the formula Ib (Ib), wherein each of m and m'independently is 0, 1 or 2, and each of R
and R' independently of the other is halogen, C1-C4alkyl, C1-C4alk-oxy or C1-C4haloalkyl.

4. 2-(2,4-Dichlorophenyl)-3-phenyl-1-(1,2,4-triazol-1H-1-yl)-propane-2,3-diol according to claim 1.

5. 2-(4-Chlorophenyl)-3-phenyl-1-(1,2,4-triazol-1H-1-yl)-propane-2,3-diol according to claim 1.

6. 2-(4-Chlorophenyl)-3-(2-chlorophenyl)-1-(1,2,4-triazol-1H-1-yl)-propane-2,3-diol according to claim 1.

7. 2-(4-Chlorophenyl)-3-para-tolyl-1-(1,2,4-triazol-1H-1-yl)-propane-2,3-diol according to claim 1.

8. 2-(4-Chlorophenyl)-3-(4-methoxyphenyl)-1-(1,2,4-triazol-1H-1-yl)-propan-2,3-diol according to claim 1.

9. 2-(4-Chlorophenyl)-3-(4-fluorophenyl)-1-(1,2,4-triazol-1H-1-yl)-propane-2,3-diol according to claim 1.

10. A 1-(imidazol-1H-1-yl)-2,3-diphenylpropane-2,3-diol according to claim 1 of the formula Ic (Ic), wherein each of m and m'independently is 0, 1 or 2 and each of R and R' independently of the other is halogen, C1-C4alkyl, C1-C4alkoxy or C1-C4haloalkyl.

11. A 1-(1,3,4-triazol-1H-1-yl)-2,3-diphenyl compound according to claim 1 of the formula Id (Id), wherein each of m and m' independently is 0, 1 or 2, each of R and R' independently of the other is halogen, C1-C4alkyl, C1-C4alkoxy or C1-C4haloalkyl, and each of R3 and R4 independently of the other is C1-C4alkyl, C1-C4alkylcarbonyl, or one of R3 and R4 is also hydrogen or both taken together form a 3- to 6-membered alkylene bridge which may be substituted by one or two C1-C4alkyl groups.

12. 2,2-Dimethyl-4-phenyl-5-(2,4-dichlorophenyl)-3-(1,2,4-triazol-1H-1-ylmethyl)-1,3-dioxolane according to claim 1 of the formula

13. 1-(1,3,4-Triazol-1H-1-yl)-2-(2,4-dichlorophenyl)-2-methoxy-3-phenylpropan-3-ol according to claim 1.

14. A process for the preparation of a 3-diazolyl- or 3-triazolyl-1,2-diphenylpropane compound of the formula I, which comprises reducing a compound of formula III

(III), wherein E, m, m', R, R', R1 and R2 are as defined in claim 1, in an inerc organic solvent, with a complex metal hydride or with hydrogen and a catalyst, with a lithium(alkyl) compound LiR5 or with an alkylmagnesium halide R5MgHal, and alkylating the resulting diol of formula IV

(IV), wherein E, m, m', R, R', R1, R2 and R5 are as defined in claim 1, in one or two steps with one mole of each of a compound R3-X and R4-X, which can be identical, optionally in an inert organic solvent and in the presence of the equimolar amount of a base as acid acceptor, or condensing the compound of formula IV, in the presence of a strong acid, with a ketone of formula V

(V) in whieh formulae above R3, R4, R6 and R7 are as defined in claim 1, and isolat-ing the product so obtained frcm the reaetion mixture.

15. A herbicidal and plant growth regulating composition which contains a 1-diazolyl- or 1-triazolyl-2,3-diphenylpropane compound of the formula I acc-ording to claim 1, together with at least one agriculturally acceptable carrier.

16. A process for the preparation of a herbicidal or plant growth re-gulating composition, whieh comprises intimately mixing a 1-diazolyl- or 1-triazolyl-2,3-diphenylpropane compound of the formula I according to claim 1, with suitable solid or liquid adjuvants and surfactants.

17. A method of controlling weeds, which comprises applying to said weeds or to the locus thereof a herbicidally effective amount of a compound of formula I according to claim 1, or of a composition according to claim 15.

18. A method of regulating plant growth, whieh comprises applying to plants or parts of plants whcse growth it is desired to influence an effective amount of a compound of formula I according to claim 1 or of a composition according to claim 15.

19. A method of selectively controlling weeds in crops of useful plants, which comprises treating said crops or the area under cultivation with an eff-ective amount of a 1-diazolyl- or 1-triazolyl-2,3-diphenylpropane compound of the formula I according to claim 1, or of a composition according to claim 15.

20. A method of selectively controlling weeds in crops of cereals, rice, sorghum and maize, which ccrprises treating said crops or the area under cultivation with an effective amount of a 1-diazolyl- or 1-triazolyl-2,3-diphen-ylpropane compound of the formula I according to claim 1, or of a composition according to claim 15.