CA1324146C - Triazole compounds - Google Patents
Triazole compoundsInfo
- Publication number
- CA1324146C CA1324146C CA000347100A CA347100A CA1324146C CA 1324146 C CA1324146 C CA 1324146C CA 000347100 A CA000347100 A CA 000347100A CA 347100 A CA347100 A CA 347100A CA 1324146 C CA1324146 C CA 1324146C
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- plant
- general formula
- seed
- triazol
- Prior art date
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- Epoxy Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
ABSTRACT
Compounds of formula:
Compounds of formula:
Description
~ 3 ~
l'~IAZOLE COMPOU~IDS, A PROCESS FOR PREPARING THEM, THEIR :
USE AS PLANT FUNGICIDES AND FUNG:I:CIDAL COMPOSITIONS
CONTAIMING THEM -,j This invention relates to triaæole compounds use~ul ~, as funyicides, to a process for preparing them, to fungi-~ cidal compositions containing them, and to a method o~
¦ combating fungal infections in plant~ using them.
¦ 5 The triazole csmpounds have the gen~ral formula (I):
:, :1 ~
J OH
- N - CH -C~
, ~ N
1 wherein R is alkyl, cycloalkyl (e.g. cyclopentyl or ¦~ cyclohexyl) or optionally substituted phenyl and R2 is i~ optionally substituted phenyl or optionally substituted ~ benzyl; or an acid addltion salt or metal complex thereof.
;~ ; - 10 The compounds of the invention can contain chiral centres. Such compounds are generally obtained in the form of racemic mixtures. However,- these and other mixtures can be separated into the individual isomers by i~ ~ i methods known in ~he ar~.
~The alkyl groups ca~ be a straight or branched chain group having l to 6, e.g. 1 to 4, carbon atoms; examples ;~
~ are methyl, ethyl, propyl (n- or iso-propylj and butyl i~ ~ (n , sec-, } or t.-butyl).
.': ,.^" ~ ~.':
9 "
. :', .
~3~ 3 Examples of suitable substituents for the phenyl and ~or the phenyl moiety of the benzyl are halogen ~e.g.
fl~orine, c~lo ine ~l- bromine), Cl 5 al'cyl /c.g. me~rl, ethyl, propyl (n~ or iso-propyl) and butyl (n-, sec-, 5 iso_ or t-butyl)_/, Cl 4 alkoxy (e.g. methoxy and etho~
trifluoromethyl, nitro, phen~l and phenoxy. The alkyl --moiety OL the benzyl can be ~ubstltuted ~th for example one alkyl (e.g. methyl or ethyl). Suitably the phenyl and benzyl are unsubstituted or substituted ~7ith i~ 2 or --10 3 ring substituents as defined above. Pr~ferably the benzyl and phenyl have a single ring substituent in ~he position. Examples of these groups are phenyl, benzyl, a-methylbenzyl, o-, m- or p-chlorophenyl, 2,4- or 2,Z-dichlorophenyl, o-, m- or p-fluorophenyl, 2,6-difluoro-1 15 phenyl, o-, m- or p-bromophenyl, 2-chloro-4-,luorophenyl, J 2-chloro-6-~luorophenyl, o-, rn- or p-methoxyphenyl, 2,4-dimethoxyphenyl, o-, m or p-ethoxyphenyl, o-, m- or p-nitrophenyl, o-, m- or p-methylphenyl, o-~ m- or ~
butylphenyl, o-, m- or p-trifluoromethylphenyl, o-, m- or 20 p-phenoxyphenyl, and o-, m- or p-phenylphenyl (o-, ~.- or p-biphenylyl), and the corresponding ring substituted ¦ benzyl and a-methylbenzyl groups.
-~ The salts can be salts with inorganic or o~ganic acids e.g. hydrochlGric, nitric, sulphuric~ acetic, p-1 ~5 toluenesulphonic or oxalic acid.
¦ Suita~ly the metal complex is o~e including, as the metal, copper, zinc, manganese or iron. It preferably has the general formula:
.~ _ _ , ,~
. ~ I E ~ CH2 C--R A2 Y 2 ;.~
wherein Y, Rl and R2 axe as de~ined above, M is a metal, A is an anion (e.g. a chloride, bromide, iodide, nitrate, .-`~ ~ ' --: :
3 ~ 3~ J
sulphate or phosphate anion), n is 2 or 4 and y is O or an integer of 1 to 12.
Exampies of the compounds of the invention are shown in Table I
' / , ;~'' ,. -.
~ ~ ' ' / . ' :
j ~ / .' '~
i 2 ~ 3 . .:
_ ., o , .
~i In ~ 1 ~ ~ O ~ C ~ r~ ~ ~
Z ~ ~ ~ ~ ~ ~ o U~ ~ ~ ~ ~ o ~ ~ o ~ r~ r~ r~ r ~ ~. G~ ~ ~ ~ ~ r-i ., ., o I I II , , , , , , , , I I I I I ~ I
L~l ~r ~ ~ o c~ c~ O ~ L') a~ Q C~ -i G' ~ ) o ~ C~ ~ O r.~l ~D O
~7 ~ r~r~Ir~r~ r~
,~j r ,' ''.',':
l'~IAZOLE COMPOU~IDS, A PROCESS FOR PREPARING THEM, THEIR :
USE AS PLANT FUNGICIDES AND FUNG:I:CIDAL COMPOSITIONS
CONTAIMING THEM -,j This invention relates to triaæole compounds use~ul ~, as funyicides, to a process for preparing them, to fungi-~ cidal compositions containing them, and to a method o~
¦ combating fungal infections in plant~ using them.
¦ 5 The triazole csmpounds have the gen~ral formula (I):
:, :1 ~
J OH
- N - CH -C~
, ~ N
1 wherein R is alkyl, cycloalkyl (e.g. cyclopentyl or ¦~ cyclohexyl) or optionally substituted phenyl and R2 is i~ optionally substituted phenyl or optionally substituted ~ benzyl; or an acid addltion salt or metal complex thereof.
;~ ; - 10 The compounds of the invention can contain chiral centres. Such compounds are generally obtained in the form of racemic mixtures. However,- these and other mixtures can be separated into the individual isomers by i~ ~ i methods known in ~he ar~.
~The alkyl groups ca~ be a straight or branched chain group having l to 6, e.g. 1 to 4, carbon atoms; examples ;~
~ are methyl, ethyl, propyl (n- or iso-propylj and butyl i~ ~ (n , sec-, } or t.-butyl).
.': ,.^" ~ ~.':
9 "
. :', .
~3~ 3 Examples of suitable substituents for the phenyl and ~or the phenyl moiety of the benzyl are halogen ~e.g.
fl~orine, c~lo ine ~l- bromine), Cl 5 al'cyl /c.g. me~rl, ethyl, propyl (n~ or iso-propyl) and butyl (n-, sec-, 5 iso_ or t-butyl)_/, Cl 4 alkoxy (e.g. methoxy and etho~
trifluoromethyl, nitro, phen~l and phenoxy. The alkyl --moiety OL the benzyl can be ~ubstltuted ~th for example one alkyl (e.g. methyl or ethyl). Suitably the phenyl and benzyl are unsubstituted or substituted ~7ith i~ 2 or --10 3 ring substituents as defined above. Pr~ferably the benzyl and phenyl have a single ring substituent in ~he position. Examples of these groups are phenyl, benzyl, a-methylbenzyl, o-, m- or p-chlorophenyl, 2,4- or 2,Z-dichlorophenyl, o-, m- or p-fluorophenyl, 2,6-difluoro-1 15 phenyl, o-, m- or p-bromophenyl, 2-chloro-4-,luorophenyl, J 2-chloro-6-~luorophenyl, o-, rn- or p-methoxyphenyl, 2,4-dimethoxyphenyl, o-, m or p-ethoxyphenyl, o-, m- or p-nitrophenyl, o-, m- or p-methylphenyl, o-~ m- or ~
butylphenyl, o-, m- or p-trifluoromethylphenyl, o-, m- or 20 p-phenoxyphenyl, and o-, m- or p-phenylphenyl (o-, ~.- or p-biphenylyl), and the corresponding ring substituted ¦ benzyl and a-methylbenzyl groups.
-~ The salts can be salts with inorganic or o~ganic acids e.g. hydrochlGric, nitric, sulphuric~ acetic, p-1 ~5 toluenesulphonic or oxalic acid.
¦ Suita~ly the metal complex is o~e including, as the metal, copper, zinc, manganese or iron. It preferably has the general formula:
.~ _ _ , ,~
. ~ I E ~ CH2 C--R A2 Y 2 ;.~
wherein Y, Rl and R2 axe as de~ined above, M is a metal, A is an anion (e.g. a chloride, bromide, iodide, nitrate, .-`~ ~ ' --: :
3 ~ 3~ J
sulphate or phosphate anion), n is 2 or 4 and y is O or an integer of 1 to 12.
Exampies of the compounds of the invention are shown in Table I
' / , ;~'' ,. -.
~ ~ ' ' / . ' :
j ~ / .' '~
i 2 ~ 3 . .:
_ ., o , .
~i In ~ 1 ~ ~ O ~ C ~ r~ ~ ~
Z ~ ~ ~ ~ ~ ~ o U~ ~ ~ ~ ~ o ~ ~ o ~ r~ r~ r~ r ~ ~. G~ ~ ~ ~ ~ r-i ., ., o I I II , , , , , , , , I I I I I ~ I
L~l ~r ~ ~ o c~ c~ O ~ L') a~ Q C~ -i G' ~ ) o ~ C~ ~ O r.~l ~D O
~7 ~ r~r~Ir~r~ r~
,~j r ,' ''.',':
3 _ _ N C~l . .
',i, . I~ ~ U I ~ ~ ,:
I ~ ~ U I I i~ X V 1 1~ . X ~ ' , ~
~ ~ U 'J~ D ~ . ~ N ~ U U U ~r ~i o ~ ..
~ r~ m ~ ~ C~ ~ ~ ~ I ~ C~
~3 U ~ ~ ~ _) C~ D C) ~ C,~
.~ ~:; u~ D U ~ D V Lr) ~J ~ LO m ~ ,~
'i H ~ I V I ~ ~ U U I ~ I U C ) U I ~ ~g U V : :
I~1 ~ ~ ~rl I r~ ~ ~1 1 1 1 ,1 ~ C,) I
~1 U O E4V C) C~ rcl ~ y U V ~- ~ ~ V U h 5~ OOO
. - - _ "''-' .
; ~ ' I I~r .'' :~
I I I ~ . ~5 5 . ~ . .
cr : :-: ~ ~ ~ I ~ ~ x I P: m- I ~ I u I _. I ~ . .
~;1 ~1 U~l f) U U ~) 1~ )L'l 1 1~ ~ L') . . .
r!:; ~, $ ~ I I u ~ o ~ ~w I x o 5 ~
~0 ~O U~ ~ ~ I ~ I I I I I ~ ~ ~ ~ ~ ~ ~ : ', : V O U V C~ h U ~ h ~) ~) ~ U U~ C.) ~ C.) 1~ V
_ - , :,"'"';'~
: ",' ~'~
: ' : Z : : ."., ' : ., .
:~ ~ z ~ + ::::
. ~ ~ ~ u~ ~ ~ O ~ ~
` ~ ~ o : r-l 1~~ ri r-l r~l ~~1 ~ r-l ~ rJ
~: ;
V _ _ _ _ :, .~J~
-~: ;- ~, .' .:
: j , '. ~ , ~
~ 3 ~
I
o~^~
~ r ~n ~ ~i o r'-~ ~ CO G~ O ~ U~
Z ~ r ,~ ~ CO r~i ~I r-,i ~ ~ ~ ~
~i I II I I II I i I I I I I
O ~ 0 ~ O ~ 1-- ~ ~1 0 ,i ~ ~ ) O o~:) r ~ L~ r~
~i ~ ~ ' ., ~i il i~ .~ :
:1 r~ :
i ' _ _ _ __ _ ,:.' .
.~, ~ r.~ I ':
. I~ ~:
:ll X I ~ 3 tD
~ ~ D ~ W ~ ~ I I I I I
D ~ U U U U U I (J U U U U I ~ ~ U U U
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`i ~¢ , ~ I I Y~ :':
er ~ D I I ,, :.
~1 ~ ~ ~mn W~O U~D U~ I W~G W~ m ~s ~i ~
~1 12~ Ql ~ ~ -'~'i - ~ , . ,' Z
: a ~ :
'1 O oi ~ ~ ~ In ~D r~ ~ ~ o ~~ a) ~ : ~ ; .' g . ~ ..
-- ~
.
'` ~3 ,ii 3i .", , i '' ~' ' '':`' - 6- ~?~
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o a) , _ ~
H . ~ ~ . -.
æ u ~ ~ o '.'- ~:
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~ C,,, I I ~ r X ~ u~
X ~D ~ I I a~ ~, p ...
r ~ C3 ~ ~ ~r C) U I I ~ X ~:; '1; ~ " ' Z ~1 I . ~ ~ ~D $ ~ $ I I O O ~ ~ ~ ~ :
H ~ ~Ln u~ L~l Ln C~ C,) V ~ S~
E~ m I ~ I v I c~ I I c~
Z . ~ aJ o --' .. .
O ~ ~ ) h l l l l l l l l l l l l l ~ Q ~
PI O O O O O O O O O O O O ~ O . ' ~, H s~
_ __ _______ .n _ ~_ . l l l l l a~
~¢ ~ ~ ~ ~ , ~
E~ ~ r ~ ~ ~ ~ L',-~
I I ~ ~ D I ~ I ~ . O ~ T
r) Ln Ln C) CJ ~D W Ln c~ Lt) ~ Lr~ '1 P~ ~ ~ ~ I i V c~ I X I a) ~
~ I W ~ ~ ~ ~D
e~ u ~ ~ o u c~ u c~ ~) ~ - -) ~ o ~ :
1~ ~ .
Z o ~1 ~ ') 'r Lr~ n o ~--1 ~ H ;~
r Lt~ Ln L~
o : :~
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7 - ~3 ~
The compounds of general formula (I) may be produced 3y reacting a compound of general formula (Il) or (III):
OH
CH2--C--Rl X~CH2--C--(~I) (III) in which Rl and R2 are as defined above and X is a halogen atom ~preferably a chlorine or bromine atom), ~
5 with 1,2,4-triazole either in the presence of an acid- -::
binding agent or in the form of one of its alkali metal salts in a convenient solvent. Suita~ly the compound of general formula (II) or (III) is reacted at 20-100 C with the sodium salt Gf 1,2,4-triazole (the salt can be prepared by adding either sodium hydride or sodium . methoxide to 1,2,4 triazole) in a convenient solvent such as acetonitrile, methanol, ethanol or dimethylformamide.
The product can be isolated by pouring the reaction mixture into water and recrystallising the solid formed ~ 15 from a convenient solventO
i,- : T~e compounds of general formula (II) and (III) can : be prepared by reacting a compound of general fonmula : .
a) or (IV~
O O '' X ~CH2 ~ C _ Rl X- CH2 ~C _R2 :(IVa) (IVb) , -.~ ~ : - . :. .
wherein Rlj R2 and X are as defined above wi.th~ respect~
20 lve~ly, a Griynard compound of general formula (Va) or (Vb): -:
.. .
~ ,:, I:
,: , :
:
Y- M~- R Y- M~-(Va) ~Vb) wh~rein Rl and R are as definPd above and Y is a halogen (pr~ferably chlorine, bromine or iodine) in a convenient solvent such as diethyl ether or tetrahydrofuran.
Generally a mixture o~ the compounds of general formula (II) and ~III) are obtained. For example, when a compound o~ general formula ~IVa) wherein R1 is alkyl or cycloalkyl is reacted, the compound of formula (II) generally predominates in the mixture; on th~ other hand, when R is optionally substituted phenyl, the compound of general ~ormula (I:rI) generally predominates in the mixture.
The compounds of general ~ormula ~IV) and (V) may be made by methods set out in the literature.
The salts and metal complexes o~ the compounds of ~ -general formula (I) can he prepared from the latter in known manner. For example, the complexes can be made by reacting the uncomplexed compound with a metal salt in a suitable solvent.
The compounds, salts and metal complexes are active fungicides, particularly against the diseases:-Piricularia oryzae on ric~.
Puccinia re~ondita, Puccinia striiformis and other rusts on wheat, Puccinia hordei, Puccinia striiformis and other rusts on barley, and rusts on oth~r hosts e.g. coffee, apples, vegetables and ormamental plants Plasmo~ara viticola on vines Er~siphe q~aminis (powdery mildew) on barley and wheat `~
and other powdery mildews on various hosts such as S~haerothec_ fuliqinea on cucurbits [e.g. cucumber), Podosphaera leucotricha on apples and Uncinula necator on vines ~
Helminthosp~rium spp. and ~hynchosporium spp. on cereals ~-,~ .-, .
~ 3 ~
g Cercospora arachidicola on peanuts and other Cercospora species on for example sugar beet, bananas and soya beans Botrytis cinerea (grey mould) on tomatoes, strawberries, vines and other hosts Phyto~_hora infestans (late blight) on tomatoes Venturia inaequalis (scab) on apples - -Some of the compounds have also shown a broad range of actlvities against fungi ln vitro. They have activity against various post-harvest diseases on fruit (e.gO -Penicillium digatatum and italicum on oranges and Gloeosporium musarum on bananas). Further some of the compounds are active as seed dressings against: Fusarium spp., Septoria spp., Tilletia spp. (i.e. bunt, a seed borne disease of wheat), Ustilago spp., Hel~inthos~ori~n j 15 spp. on cereals, Rhizoctonia solani on cotton and Corticium sasakii on rice.
The compounds can move acropetally in the pl~nt ~issue. Moreovex, the compounds can be volatile enough to be active in the vapour phase against fungi. on the p:Lant.
The compounds may be used as such for fungicidal I purposes but are more conveniently formulated into I compositions for such usage. The invention thus provides also a fungicidal composition comprising a compound of general formula (I) or a salt or complex thereof as hereinbefore defined, and a carrier or diluent.
The invention alio provides a method of combating ~, fungal diseases in a plant, wh~ch method comprises applying to the plant, to seed of the plant or to the j 30 locus of the plant or seed a compound or a salt or l complex thereof as hexeinbefore defined.
The compounds, salts and complexes can be applied in , a number of ways, for example they can be formulated or 1, unformulated, directly to the foliage of a plant, to ~ 35 seeds or to other medium in which plants are growing or ~, . ' ' .
-~ 10 --are to be planted, or they can be sprayed on, dusted on or applied as a cream or paste formulation, or t~,ey can be applied as a vapour. Application can be to any part of the plant, bush or tree, for example to the foliage, stems, branches or roots, or to soil surrounding the roots, or to the seed before it is planted.
The term "plant" as used herein includes seedlings, bushes and trees. Furthermore, the fungicldal method of he invention includes preventative, protectant, prophylactic and eradicant treatment.
The compounds are preferably used for agricultural and horticultural purposes in the form of a composi~ion.
; The type of composition used in any instance will depend upon the particular purpose envisaged.
15The compcsitions may be in the form of dusting powders or granules compxising the ac'cive ingredient and a solid diluent or carrier, for example fillers such as kaolin, bentonite, kieselguhr, dolomite~ calcium carbon-ate, talc, powdered magnesia, ~uller's earth, gypsum, ~I 20 Hewitt's earth, diatomaceous earth and China clay. Such granules can he preformed granules suitable for application to the soil without further treatment. These granules can be made either by impregnating pellets of filler with the active ingredient or by pelleting a mixture of the active ingredient and powdered filler. Compositions for ~ dressing seed, for example, may comprise an a~ent (for example a mineral oil) for assisting the adhesion of the composition to the seed; alt~rnatively the active ingred-ient can be formulated for seed dressing purposes using an organic sol~ent (for example N-methylpyrrolidone or dimethylformamide).
The compositions may also be in the form of dis-persible powders, granules or grains comprising a wetting agent to facilltate the dispersion in liquids of the powder or gxains which may contain also fillers and j suspending agents.
:'j :
.
~ 3 2 -~ ~ Ls~ J~
The aqueous dispersions or emulsions may be prepared by dissolvinq the active inqredient(s) in an organic solvent optionall~ containing wetting, dispersing or emulsifying agent(s) and then adding the rnixture to water which may also contain wetting, dispersing or emulsifying agent(s). Suitable organic solvents are ethylene dichloride, isopropyl alcohol, propylene glycol, di~
acetone alcohol, toluene, kerosene, methylnaphthalene, the xylenes, trichloroethylene, furfuryl alcohol, tetra-hydrofurfuryl alcohol, and glycol ethers (e.g. 2-ethoxy-ethanol and 2-butoxyethanol).
The compositions to be used as sprays may also be in the form of aerosols wherein the formulation is held in a container under pressure in the presence of a propellant, e.g. fluorotrichloromethane or dichlorodifluoromethane.
The compounds can be mixed in the dry state with a pyrotechnic mixture to form a composition suitable for ;
generating in enclosed spaces a smoke containing the compounds.
1 20 Alternatively, the compouncls may be used in a micro-encapsulated form.
~ By including suitable additives, for example additives 1` for improving the distribution, adhesive power and I resistance to rain on treated surfaces, the different j 25 compositions can be better adapted for various utilities.
The compounds can be used as mixtures with ferti- I
lisers (e.g. nitrogen-, potassiumi- or phosphorus-containing ' fertilisers). Compositions comprising only granules of ~-~
~ ~ertiliiser incorporating, for example coated with, the j ~ 30 compound, are preferred~ Such granules suitably contain ~ii up to 25~ by weight of the compound. The invention 1 ~ thexefore also provides a fer-tiliser composition comprising l~ ` the compound of yeneral formula (I) or a salt or metal complex thereof.
The compositions may also be in the form of liquid -~
? preparations or usei as dips or sprays which are generally -.
.~ . :
.1, . ' , :,:
- 12 ~ L ~ ~ ~
aqueous dispersions or emulsions cortaining the active ir.gredie~t in the presence or one or more surfactants e.g. wetting agent(s), dispersing agent(s), emulsifying agent(s) or suspending agent(s). These agents can be cationic, anionic or non-ionic agents. Suitable cationic agents are quaternary ammonium compounds, for example cetyltrimethylammonium bromide.
Suitable anionic agents are soaps, salts of aliphatic monoesters of sulphurlc acid (for example sodium lauryl sulpha-te), and salts of sulphonated aromatic compounds (for example sodium dodecylbenzenesulphonate, sodium, calcium or ammonium lignosulphonate~ butylnaphthalene sulphonate, and a mixture of sodium diisopropyl- and triisopropyl-naphthalene sulphonates).
]5 Suitable non-ionic agents are the condansation products of ethylene oxide with fatty alcohols such as oleyl or cetyl alcohol, or with alkyl phenols such as octyl- or nonyl-phenol and octylcresol. Other non-ionic agents are the partial esters derived from long chain fatty acids and hexitol anhydrides, the condensation products of the said partial esters with ethylene oxide, and the lecithins. Suitable suspending agents are hydrophilic colloids (for example polyvinylpyrrolidone and sodium carboxymethylcellulose), and the vegetable gums (for example gum acacia and gum tragacanth~.
'l The compositions for use as aqueous dispersions or i emulsions are general-ly supplied in the form of a concen-trate containing a high proportion of the active ingred- -ient(s), the concentrate to be diluted with water before use. These concentrates often should be able -to with-, stand storage for prolonged periods and after such - storage be capable of dilution with water in order to : 3 form aqu20us preparations which remain homogeneous for a sufficient time to enable them to be applied by conventional spray equipment. The concentrates may conveniently contain up to 95%, suitably 10-85%, for example 25-60%, ~,~ . ,:
:, , . .:
. ' ': .
by weight of the active ingredient(s~. These concentrates suitably contain organic acids (e.y. alkaryl or aryl sulphonic acids such as xylenesulphonic acid or dodecylbenzenesulphonic acid) since the presence of such acids can increase the solubility of the active ingredient(s) in the polar solvents often used in the concentrates. The concentrates suitably contain also a high proportion of surfactants so that sufficiently stable emulsions in water can be obtained. After ~ilution -to ~orm aqueous preparations, such preparations may contain varying amounts of the active ingredient(s) depending upon the intended purpose, but an aqueous preparation containing 0~0005~ or 0.01~ to 10% by weight of active inyredient(s) may be used.
The compositions of this invention can comprise also other compoundts~ having biological activity, e.g.
compounds having similar or complementary fungicidal activity or compounds having plant growth regulating, herbicidal or insecticidal acti~ity.
The other fungicidal compound can be for example one which is capable of combating ear diseases of cereals (e.g. wheat~ such as Septoria, Gibberella and - ~
~el~i~tb~ ri~ spp., seed and soil borne disease and ~--downy and powdery mildews on grapes and powdery mildew ~- ~
and scab on apple etc. These mixtures of fungicides can -have a broader spectrum of activity than the compound of general Formula (I) alone: further the other fungicide ;~
can have a synergistic ef~ect on the fungicidal activity of the compound of general formula (I). Examples of the other fungicidal compound are imazalil, benomyl, carbendazim ~BCM), thiophanate-methyl, captafol, captan, sulphur, dithiocarbamates, carbathiins, copper oxychlorid~, triforine, dodemorph, tridemorph, dithianon, pyrazophos, binapacryl, quinomethionate, panoctine, furalax~l, aluminium tris(ethylphosphonate), ~PX3217, ethirimol, . .
. '.;
:: ' ~32~
dimethirimol, bupirimate, chlorothalonil, Ch~vron RE 20615*, vinclozolin, procymidone, iprodione, metaxanine, dichlobutrazol and thiabendazol.
The compounds of general formula ~I) can be mixed with -soil, peat or other rooting media for the protection o~ plants against seed-borne, soil-borne or foliar fungal diseases.
Suitable insecticides are pirimor, croneton, dimethoate, `-metasystox and formothion.
Examples o~ suitable plant growth regulating compounds are the gibberellins (e.g. GA3, GA4 or GA7~, the auxins (e.g.
indoleacetic acid, indolebutyric acid, naphthoxyacetic acid or naphthylacetic acid~, the cytokinins ~e.g~ kinetinr diphenylurea, benzimidazole, benzyladenine or BAP), phenoxyacetic acids te.g.
2,4-D or m-chlorophenoxyacetic acid~, substituted benzoic acids (e.g. trib~lobenzoic acid), morphactins (e.g. chlorfluorecol), I maleic hydrazide, glyphosate, glyphosine, long chain fatty ~ alcohols and acids (e.g. Off Shoot O or Off Shoot T~, dikegulac, ¦ Sustar, Embark, substituted quaternclry ammonium and phosphonium ! compounds (e~g. CCC or Phosfon-D), Ethrel, carbetamide, Racuza, Alar, asulam, abscissic acid, isopyrimol, RH531*, hydroxy-¦ henzonitriles (e.g~ bromoxynil), Avenge, Suffix or Lontrel.
1 The following Examples illust~ate the invention; the ¦ temperatures are given in degrees Centigrade ~C).
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EXAl~PLE 1 1-(1,2,4-Triazol~l-yl)-2,3-diphenyl~propan-2-ol Benzyl chloride (0.2 mol) was dissolvPd in dry diethyl ether (200 ml) and added dropwise to magnesium turnings ~0.22 g atoms). After all the magnesium had reacted, ~he solution was rPfluxed for l hour and cooled to room temperature. Phenacyl chloride (0.1 mol) in dry diethyl ether (lO0 ml) was added dropwise over 1 hour at such a rate as to maintain gentle reflux. The solution was then refluxed for 2 hours, and cooled to room tem- ~;
perature; the mixture was poured into ice and the , lO complex decomposed with ammonium chloride solution. The ! ethereal solukion was washed several times with water (2 x 200 ml), dried (Na2S0~), and the solvent removed in vacuo to give, as a colourless o:il, the crude chlorohydrin which was dissolved in dimethyl formamide (80 ml) and a ~ -solution of sodium triazole ~ prepared from sodium ¦ ~0.1 g atoms~ in methanol (4P ml) and 1,2,4-triazole (0.1 mol) / added dropwise at room temperature. After stirring at room temperature ~or 2 hours, the solution was warmed a~ 50 for 3 hours. rrhe solvent was removed ln vacuo and the residue poured :Lnto water to give a crystalline solid which was recrystallised from ethanol/
petroleum ether to give the ~itle compound, m.p. 124.5.
~ : -,:
: I ~
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- 16 - ~ 3 ~ ~ ~ *3 1-(1,2,4-Triazol-l-yl)-2-phenyl-3-p-fluorophenyl-propan- --2-ol p-Fluorobenzyl chloride (0.1 mol~ in dry diethyl ether (100 ml) was added dropwise to magnesium turninys (0.11 g atoms) and the .solution stirred vigorously until' refluxing occurred. When all the magnesium had reacted, 5 the solution was refluxed for a further 1 hour and then cooled to room temperature. Phenacyl chloride (0.05 mol) in dry diethyl ether (50 ml) was added dropwise to the solution over 1 hour at such a rate as to maintain gentle reflux. The mixture was refluxed for 2 hours, cooled to room temperature and the mixture poured into ice/ammonium chloride solution to decompose the complex. The ethereal solution was washed several tim~!s with watar (2 x 200 ml), drled (Na2S04), and the solvent removed in vacuo to give, as a colourless oil, the crude chlorohydrin. The latter was dissol~ed in dimethylformamlde (~0 ml) and a solution of sodium triazole / prepared from sodium (0.05 g atoms) in methanol ~20 ml) and 1,2,4-briazole (0.05 mol) ~
added dropwise at room temperature. After stirring at ~ oom temperature for 2 hours, the solution was warmed at I ~ 20 50 for 3 hours. The solvent was removed in vacuo and !: ~ the mixture poured into water to give a crystalline solid which was recrystallised from petroleum ether/chloroform to gi.e the tLtle compound, m.p. 116-8. - -~ ~ ~ a-L .'1 'q. -~
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2 4-triazol-1-y~L-2 2-diphenyl-ethan-2-ol (Compound 17) Staqe 1. Bromobenzene (0.2 mol, 31.4 g) in sodium dry diethyl ether (200 ml) was added dropwise to magnesium (0.22 gra~ atoms, 5.3 g). ~fter all the magnesium had ~ -reacted, phenacyl chloride (0.1 mol, 1~.5 g) in diethyl ether (100 ml) was added dropwise and the solution stirred at room temperature for 1 hour. The reaction mixtur~ was poured into saturated ammonium chloride solution, washed with water (3 x 150 ml), and dried (NazSO4)~ Removal of the ether gave a pale yellow oil which ~olidified on standing. Recrystallisation from petroleum ether (60-80) gave l,l-diphenyl-2-chloro-ethan-l-ol (60%) as a white crystalline solid, m.p. 56-'.'.~ :,' _ta~e 2. 1,2,4-Triazole (0.03 mol., 2.07 y) was added portionwise to a suspension of sodium hydride (0.03 mol, 0.72 g) in DMF (30 ml~ and the s~olution stirred until effervescence ceased. l,l-Diph~nyl-2-chloro-ethan-1-ol (0.015 mol, 2.94 g~ in dimethylformamide (DMF; 10 ml) was added dropwise and the solution warmed at 100 for six hours. The reaction mixture was poured into water and a white solid crystallised out~ This was filtered off, washed with water, dried, and recrystallised from ethanol ;~
to give th~ title compound as a white crystalline solid, m.p~ 128 129.
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1 L1,2,4-triazol-1~ 2-Phenyl-~ methyl-pentan-2-ol (Compound 31) Staqe 1. The Grignard reagent generated from isobutyl bromide (0~1 mol, 13.7 g~ in sodium dry diethyl ether (50 ml~ and magnesium turnings (0.11 g atoms; 2.6 g) was added dropwise to a solution of phenacyl chloride (0.05 moll 757 g) in sodium dry diethyl ether (100 ml) so that gentle re~lux was maintained. The solution was then stirred at room temperature ~or 1 hour and the magnesium complex destroyed by pouring into a saturated ammonium chloride solution (200 ml). The ethereal extract was washed with water (3 x 150 ml) ~nd dried ~Na2S04).
Removal of the solvent gave a colourless liquid which distilled at reduced pressure to give 2-methyl~4-phenyl~
15 5~chloro-pentan-4-01 (70%3, b.p. 86-88/0.01 mm Hg.
Sta~ . 1,2,4-Triazole (O.03 mol, 2.07 g) was added portionwise to 100% sodium hydride (0.03 mol, 0.72 g) in dry DMF (30 ml) and stirred at room temperature until the effervescence ceased. 2-Methyl-4-phenyl-5-chloro-pentan-20 4-ol (0.01 mol, 2.~ g) in dry DMF (10 ml~ was added dropwise at room temperature and then the solution was stirred at 100~ for 6 hours. On cooling to room temperature khe solu~ion was poured in~o wa~er to precipitate out a solid which wa~ recrystallis~d from petroleum (60-80)/chloroform giving the title compound (60%) as a white solid crystalline solid, m.p. 94-95.
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'. ~' - 19 - ~ 3 ~ 73 The compounds were tested against a variety of foliar fungal diseases of plants. The technique employed was as follows.
The plants were grown in John Innes Potting Compost (No 1 or 2) in 4 cm diameter minipots. A layer of fine sand was placed at the bottom of the pots containing the dicotyledonous plants to facilitate uptake of test compound by the roots~ The test compounds werP formulated either by bead milling with aqueous Dispersol T or as a solution in acetone or acetone/ethanol which was diluted to the required concentration immediately before use.
For the foliage diseases, suspensions (lO0 ppm active ingredient) were sprayed on to the soil. Exceptions to this were the tests on ~ cinerea, Plasmopara viticola and Venturia inaequalis. The sprays were applied to maximum retention and the root drenches to a final concentration equivalent to approximately 40 ppm a.i./
dry soil. Tween 20, to give a final concentration of 0.05%, was added when the sprays were applied to cereals.
For most of the tests the co~pound was applied to the soil (roots) and to the foliage (by spraying) one or two days before the plant was inoculated with the di~eases. An excepti~n was the test on Erysiphe graminis in which the plants were inoculated 24 hours before treat-ment. ~fter inoculation, the plants were put into an appropriate environment to allow infection to take place and then incubated until the disease was ready for assessment. The period between inoculation and assess-ment varied from four to fourteen days according to the 30 disease and environment. -~
The disease control was recorded by the following grading~
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The compounds of general formula (I) may be produced 3y reacting a compound of general formula (Il) or (III):
OH
CH2--C--Rl X~CH2--C--(~I) (III) in which Rl and R2 are as defined above and X is a halogen atom ~preferably a chlorine or bromine atom), ~
5 with 1,2,4-triazole either in the presence of an acid- -::
binding agent or in the form of one of its alkali metal salts in a convenient solvent. Suita~ly the compound of general formula (II) or (III) is reacted at 20-100 C with the sodium salt Gf 1,2,4-triazole (the salt can be prepared by adding either sodium hydride or sodium . methoxide to 1,2,4 triazole) in a convenient solvent such as acetonitrile, methanol, ethanol or dimethylformamide.
The product can be isolated by pouring the reaction mixture into water and recrystallising the solid formed ~ 15 from a convenient solventO
i,- : T~e compounds of general formula (II) and (III) can : be prepared by reacting a compound of general fonmula : .
a) or (IV~
O O '' X ~CH2 ~ C _ Rl X- CH2 ~C _R2 :(IVa) (IVb) , -.~ ~ : - . :. .
wherein Rlj R2 and X are as defined above wi.th~ respect~
20 lve~ly, a Griynard compound of general formula (Va) or (Vb): -:
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Y- M~- R Y- M~-(Va) ~Vb) wh~rein Rl and R are as definPd above and Y is a halogen (pr~ferably chlorine, bromine or iodine) in a convenient solvent such as diethyl ether or tetrahydrofuran.
Generally a mixture o~ the compounds of general formula (II) and ~III) are obtained. For example, when a compound o~ general formula ~IVa) wherein R1 is alkyl or cycloalkyl is reacted, the compound of formula (II) generally predominates in the mixture; on th~ other hand, when R is optionally substituted phenyl, the compound of general ~ormula (I:rI) generally predominates in the mixture.
The compounds of general ~ormula ~IV) and (V) may be made by methods set out in the literature.
The salts and metal complexes o~ the compounds of ~ -general formula (I) can he prepared from the latter in known manner. For example, the complexes can be made by reacting the uncomplexed compound with a metal salt in a suitable solvent.
The compounds, salts and metal complexes are active fungicides, particularly against the diseases:-Piricularia oryzae on ric~.
Puccinia re~ondita, Puccinia striiformis and other rusts on wheat, Puccinia hordei, Puccinia striiformis and other rusts on barley, and rusts on oth~r hosts e.g. coffee, apples, vegetables and ormamental plants Plasmo~ara viticola on vines Er~siphe q~aminis (powdery mildew) on barley and wheat `~
and other powdery mildews on various hosts such as S~haerothec_ fuliqinea on cucurbits [e.g. cucumber), Podosphaera leucotricha on apples and Uncinula necator on vines ~
Helminthosp~rium spp. and ~hynchosporium spp. on cereals ~-,~ .-, .
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g Cercospora arachidicola on peanuts and other Cercospora species on for example sugar beet, bananas and soya beans Botrytis cinerea (grey mould) on tomatoes, strawberries, vines and other hosts Phyto~_hora infestans (late blight) on tomatoes Venturia inaequalis (scab) on apples - -Some of the compounds have also shown a broad range of actlvities against fungi ln vitro. They have activity against various post-harvest diseases on fruit (e.gO -Penicillium digatatum and italicum on oranges and Gloeosporium musarum on bananas). Further some of the compounds are active as seed dressings against: Fusarium spp., Septoria spp., Tilletia spp. (i.e. bunt, a seed borne disease of wheat), Ustilago spp., Hel~inthos~ori~n j 15 spp. on cereals, Rhizoctonia solani on cotton and Corticium sasakii on rice.
The compounds can move acropetally in the pl~nt ~issue. Moreovex, the compounds can be volatile enough to be active in the vapour phase against fungi. on the p:Lant.
The compounds may be used as such for fungicidal I purposes but are more conveniently formulated into I compositions for such usage. The invention thus provides also a fungicidal composition comprising a compound of general formula (I) or a salt or complex thereof as hereinbefore defined, and a carrier or diluent.
The invention alio provides a method of combating ~, fungal diseases in a plant, wh~ch method comprises applying to the plant, to seed of the plant or to the j 30 locus of the plant or seed a compound or a salt or l complex thereof as hexeinbefore defined.
The compounds, salts and complexes can be applied in , a number of ways, for example they can be formulated or 1, unformulated, directly to the foliage of a plant, to ~ 35 seeds or to other medium in which plants are growing or ~, . ' ' .
-~ 10 --are to be planted, or they can be sprayed on, dusted on or applied as a cream or paste formulation, or t~,ey can be applied as a vapour. Application can be to any part of the plant, bush or tree, for example to the foliage, stems, branches or roots, or to soil surrounding the roots, or to the seed before it is planted.
The term "plant" as used herein includes seedlings, bushes and trees. Furthermore, the fungicldal method of he invention includes preventative, protectant, prophylactic and eradicant treatment.
The compounds are preferably used for agricultural and horticultural purposes in the form of a composi~ion.
; The type of composition used in any instance will depend upon the particular purpose envisaged.
15The compcsitions may be in the form of dusting powders or granules compxising the ac'cive ingredient and a solid diluent or carrier, for example fillers such as kaolin, bentonite, kieselguhr, dolomite~ calcium carbon-ate, talc, powdered magnesia, ~uller's earth, gypsum, ~I 20 Hewitt's earth, diatomaceous earth and China clay. Such granules can he preformed granules suitable for application to the soil without further treatment. These granules can be made either by impregnating pellets of filler with the active ingredient or by pelleting a mixture of the active ingredient and powdered filler. Compositions for ~ dressing seed, for example, may comprise an a~ent (for example a mineral oil) for assisting the adhesion of the composition to the seed; alt~rnatively the active ingred-ient can be formulated for seed dressing purposes using an organic sol~ent (for example N-methylpyrrolidone or dimethylformamide).
The compositions may also be in the form of dis-persible powders, granules or grains comprising a wetting agent to facilltate the dispersion in liquids of the powder or gxains which may contain also fillers and j suspending agents.
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The aqueous dispersions or emulsions may be prepared by dissolvinq the active inqredient(s) in an organic solvent optionall~ containing wetting, dispersing or emulsifying agent(s) and then adding the rnixture to water which may also contain wetting, dispersing or emulsifying agent(s). Suitable organic solvents are ethylene dichloride, isopropyl alcohol, propylene glycol, di~
acetone alcohol, toluene, kerosene, methylnaphthalene, the xylenes, trichloroethylene, furfuryl alcohol, tetra-hydrofurfuryl alcohol, and glycol ethers (e.g. 2-ethoxy-ethanol and 2-butoxyethanol).
The compositions to be used as sprays may also be in the form of aerosols wherein the formulation is held in a container under pressure in the presence of a propellant, e.g. fluorotrichloromethane or dichlorodifluoromethane.
The compounds can be mixed in the dry state with a pyrotechnic mixture to form a composition suitable for ;
generating in enclosed spaces a smoke containing the compounds.
1 20 Alternatively, the compouncls may be used in a micro-encapsulated form.
~ By including suitable additives, for example additives 1` for improving the distribution, adhesive power and I resistance to rain on treated surfaces, the different j 25 compositions can be better adapted for various utilities.
The compounds can be used as mixtures with ferti- I
lisers (e.g. nitrogen-, potassiumi- or phosphorus-containing ' fertilisers). Compositions comprising only granules of ~-~
~ ~ertiliiser incorporating, for example coated with, the j ~ 30 compound, are preferred~ Such granules suitably contain ~ii up to 25~ by weight of the compound. The invention 1 ~ thexefore also provides a fer-tiliser composition comprising l~ ` the compound of yeneral formula (I) or a salt or metal complex thereof.
The compositions may also be in the form of liquid -~
? preparations or usei as dips or sprays which are generally -.
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aqueous dispersions or emulsions cortaining the active ir.gredie~t in the presence or one or more surfactants e.g. wetting agent(s), dispersing agent(s), emulsifying agent(s) or suspending agent(s). These agents can be cationic, anionic or non-ionic agents. Suitable cationic agents are quaternary ammonium compounds, for example cetyltrimethylammonium bromide.
Suitable anionic agents are soaps, salts of aliphatic monoesters of sulphurlc acid (for example sodium lauryl sulpha-te), and salts of sulphonated aromatic compounds (for example sodium dodecylbenzenesulphonate, sodium, calcium or ammonium lignosulphonate~ butylnaphthalene sulphonate, and a mixture of sodium diisopropyl- and triisopropyl-naphthalene sulphonates).
]5 Suitable non-ionic agents are the condansation products of ethylene oxide with fatty alcohols such as oleyl or cetyl alcohol, or with alkyl phenols such as octyl- or nonyl-phenol and octylcresol. Other non-ionic agents are the partial esters derived from long chain fatty acids and hexitol anhydrides, the condensation products of the said partial esters with ethylene oxide, and the lecithins. Suitable suspending agents are hydrophilic colloids (for example polyvinylpyrrolidone and sodium carboxymethylcellulose), and the vegetable gums (for example gum acacia and gum tragacanth~.
'l The compositions for use as aqueous dispersions or i emulsions are general-ly supplied in the form of a concen-trate containing a high proportion of the active ingred- -ient(s), the concentrate to be diluted with water before use. These concentrates often should be able -to with-, stand storage for prolonged periods and after such - storage be capable of dilution with water in order to : 3 form aqu20us preparations which remain homogeneous for a sufficient time to enable them to be applied by conventional spray equipment. The concentrates may conveniently contain up to 95%, suitably 10-85%, for example 25-60%, ~,~ . ,:
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by weight of the active ingredient(s~. These concentrates suitably contain organic acids (e.y. alkaryl or aryl sulphonic acids such as xylenesulphonic acid or dodecylbenzenesulphonic acid) since the presence of such acids can increase the solubility of the active ingredient(s) in the polar solvents often used in the concentrates. The concentrates suitably contain also a high proportion of surfactants so that sufficiently stable emulsions in water can be obtained. After ~ilution -to ~orm aqueous preparations, such preparations may contain varying amounts of the active ingredient(s) depending upon the intended purpose, but an aqueous preparation containing 0~0005~ or 0.01~ to 10% by weight of active inyredient(s) may be used.
The compositions of this invention can comprise also other compoundts~ having biological activity, e.g.
compounds having similar or complementary fungicidal activity or compounds having plant growth regulating, herbicidal or insecticidal acti~ity.
The other fungicidal compound can be for example one which is capable of combating ear diseases of cereals (e.g. wheat~ such as Septoria, Gibberella and - ~
~el~i~tb~ ri~ spp., seed and soil borne disease and ~--downy and powdery mildews on grapes and powdery mildew ~- ~
and scab on apple etc. These mixtures of fungicides can -have a broader spectrum of activity than the compound of general Formula (I) alone: further the other fungicide ;~
can have a synergistic ef~ect on the fungicidal activity of the compound of general formula (I). Examples of the other fungicidal compound are imazalil, benomyl, carbendazim ~BCM), thiophanate-methyl, captafol, captan, sulphur, dithiocarbamates, carbathiins, copper oxychlorid~, triforine, dodemorph, tridemorph, dithianon, pyrazophos, binapacryl, quinomethionate, panoctine, furalax~l, aluminium tris(ethylphosphonate), ~PX3217, ethirimol, . .
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dimethirimol, bupirimate, chlorothalonil, Ch~vron RE 20615*, vinclozolin, procymidone, iprodione, metaxanine, dichlobutrazol and thiabendazol.
The compounds of general formula ~I) can be mixed with -soil, peat or other rooting media for the protection o~ plants against seed-borne, soil-borne or foliar fungal diseases.
Suitable insecticides are pirimor, croneton, dimethoate, `-metasystox and formothion.
Examples o~ suitable plant growth regulating compounds are the gibberellins (e.g. GA3, GA4 or GA7~, the auxins (e.g.
indoleacetic acid, indolebutyric acid, naphthoxyacetic acid or naphthylacetic acid~, the cytokinins ~e.g~ kinetinr diphenylurea, benzimidazole, benzyladenine or BAP), phenoxyacetic acids te.g.
2,4-D or m-chlorophenoxyacetic acid~, substituted benzoic acids (e.g. trib~lobenzoic acid), morphactins (e.g. chlorfluorecol), I maleic hydrazide, glyphosate, glyphosine, long chain fatty ~ alcohols and acids (e.g. Off Shoot O or Off Shoot T~, dikegulac, ¦ Sustar, Embark, substituted quaternclry ammonium and phosphonium ! compounds (e~g. CCC or Phosfon-D), Ethrel, carbetamide, Racuza, Alar, asulam, abscissic acid, isopyrimol, RH531*, hydroxy-¦ henzonitriles (e.g~ bromoxynil), Avenge, Suffix or Lontrel.
1 The following Examples illust~ate the invention; the ¦ temperatures are given in degrees Centigrade ~C).
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EXAl~PLE 1 1-(1,2,4-Triazol~l-yl)-2,3-diphenyl~propan-2-ol Benzyl chloride (0.2 mol) was dissolvPd in dry diethyl ether (200 ml) and added dropwise to magnesium turnings ~0.22 g atoms). After all the magnesium had reacted, ~he solution was rPfluxed for l hour and cooled to room temperature. Phenacyl chloride (0.1 mol) in dry diethyl ether (lO0 ml) was added dropwise over 1 hour at such a rate as to maintain gentle reflux. The solution was then refluxed for 2 hours, and cooled to room tem- ~;
perature; the mixture was poured into ice and the , lO complex decomposed with ammonium chloride solution. The ! ethereal solukion was washed several times with water (2 x 200 ml), dried (Na2S0~), and the solvent removed in vacuo to give, as a colourless o:il, the crude chlorohydrin which was dissolved in dimethyl formamide (80 ml) and a ~ -solution of sodium triazole ~ prepared from sodium ¦ ~0.1 g atoms~ in methanol (4P ml) and 1,2,4-triazole (0.1 mol) / added dropwise at room temperature. After stirring at room temperature ~or 2 hours, the solution was warmed a~ 50 for 3 hours. rrhe solvent was removed ln vacuo and the residue poured :Lnto water to give a crystalline solid which was recrystallised from ethanol/
petroleum ether to give the ~itle compound, m.p. 124.5.
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- 16 - ~ 3 ~ ~ ~ *3 1-(1,2,4-Triazol-l-yl)-2-phenyl-3-p-fluorophenyl-propan- --2-ol p-Fluorobenzyl chloride (0.1 mol~ in dry diethyl ether (100 ml) was added dropwise to magnesium turninys (0.11 g atoms) and the .solution stirred vigorously until' refluxing occurred. When all the magnesium had reacted, 5 the solution was refluxed for a further 1 hour and then cooled to room temperature. Phenacyl chloride (0.05 mol) in dry diethyl ether (50 ml) was added dropwise to the solution over 1 hour at such a rate as to maintain gentle reflux. The mixture was refluxed for 2 hours, cooled to room temperature and the mixture poured into ice/ammonium chloride solution to decompose the complex. The ethereal solution was washed several tim~!s with watar (2 x 200 ml), drled (Na2S04), and the solvent removed in vacuo to give, as a colourless oil, the crude chlorohydrin. The latter was dissol~ed in dimethylformamlde (~0 ml) and a solution of sodium triazole / prepared from sodium (0.05 g atoms) in methanol ~20 ml) and 1,2,4-briazole (0.05 mol) ~
added dropwise at room temperature. After stirring at ~ oom temperature for 2 hours, the solution was warmed at I ~ 20 50 for 3 hours. The solvent was removed in vacuo and !: ~ the mixture poured into water to give a crystalline solid which was recrystallised from petroleum ether/chloroform to gi.e the tLtle compound, m.p. 116-8. - -~ ~ ~ a-L .'1 'q. -~
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2 4-triazol-1-y~L-2 2-diphenyl-ethan-2-ol (Compound 17) Staqe 1. Bromobenzene (0.2 mol, 31.4 g) in sodium dry diethyl ether (200 ml) was added dropwise to magnesium (0.22 gra~ atoms, 5.3 g). ~fter all the magnesium had ~ -reacted, phenacyl chloride (0.1 mol, 1~.5 g) in diethyl ether (100 ml) was added dropwise and the solution stirred at room temperature for 1 hour. The reaction mixtur~ was poured into saturated ammonium chloride solution, washed with water (3 x 150 ml), and dried (NazSO4)~ Removal of the ether gave a pale yellow oil which ~olidified on standing. Recrystallisation from petroleum ether (60-80) gave l,l-diphenyl-2-chloro-ethan-l-ol (60%) as a white crystalline solid, m.p. 56-'.'.~ :,' _ta~e 2. 1,2,4-Triazole (0.03 mol., 2.07 y) was added portionwise to a suspension of sodium hydride (0.03 mol, 0.72 g) in DMF (30 ml~ and the s~olution stirred until effervescence ceased. l,l-Diph~nyl-2-chloro-ethan-1-ol (0.015 mol, 2.94 g~ in dimethylformamide (DMF; 10 ml) was added dropwise and the solution warmed at 100 for six hours. The reaction mixture was poured into water and a white solid crystallised out~ This was filtered off, washed with water, dried, and recrystallised from ethanol ;~
to give th~ title compound as a white crystalline solid, m.p~ 128 129.
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1 L1,2,4-triazol-1~ 2-Phenyl-~ methyl-pentan-2-ol (Compound 31) Staqe 1. The Grignard reagent generated from isobutyl bromide (0~1 mol, 13.7 g~ in sodium dry diethyl ether (50 ml~ and magnesium turnings (0.11 g atoms; 2.6 g) was added dropwise to a solution of phenacyl chloride (0.05 moll 757 g) in sodium dry diethyl ether (100 ml) so that gentle re~lux was maintained. The solution was then stirred at room temperature ~or 1 hour and the magnesium complex destroyed by pouring into a saturated ammonium chloride solution (200 ml). The ethereal extract was washed with water (3 x 150 ml) ~nd dried ~Na2S04).
Removal of the solvent gave a colourless liquid which distilled at reduced pressure to give 2-methyl~4-phenyl~
15 5~chloro-pentan-4-01 (70%3, b.p. 86-88/0.01 mm Hg.
Sta~ . 1,2,4-Triazole (O.03 mol, 2.07 g) was added portionwise to 100% sodium hydride (0.03 mol, 0.72 g) in dry DMF (30 ml) and stirred at room temperature until the effervescence ceased. 2-Methyl-4-phenyl-5-chloro-pentan-20 4-ol (0.01 mol, 2.~ g) in dry DMF (10 ml~ was added dropwise at room temperature and then the solution was stirred at 100~ for 6 hours. On cooling to room temperature khe solu~ion was poured in~o wa~er to precipitate out a solid which wa~ recrystallis~d from petroleum (60-80)/chloroform giving the title compound (60%) as a white solid crystalline solid, m.p. 94-95.
'''~;''"
,: ~
;~ .. " .
'. ~' - 19 - ~ 3 ~ 73 The compounds were tested against a variety of foliar fungal diseases of plants. The technique employed was as follows.
The plants were grown in John Innes Potting Compost (No 1 or 2) in 4 cm diameter minipots. A layer of fine sand was placed at the bottom of the pots containing the dicotyledonous plants to facilitate uptake of test compound by the roots~ The test compounds werP formulated either by bead milling with aqueous Dispersol T or as a solution in acetone or acetone/ethanol which was diluted to the required concentration immediately before use.
For the foliage diseases, suspensions (lO0 ppm active ingredient) were sprayed on to the soil. Exceptions to this were the tests on ~ cinerea, Plasmopara viticola and Venturia inaequalis. The sprays were applied to maximum retention and the root drenches to a final concentration equivalent to approximately 40 ppm a.i./
dry soil. Tween 20, to give a final concentration of 0.05%, was added when the sprays were applied to cereals.
For most of the tests the co~pound was applied to the soil (roots) and to the foliage (by spraying) one or two days before the plant was inoculated with the di~eases. An excepti~n was the test on Erysiphe graminis in which the plants were inoculated 24 hours before treat-ment. ~fter inoculation, the plants were put into an appropriate environment to allow infection to take place and then incubated until the disease was ready for assessment. The period between inoculation and assess-ment varied from four to fourteen days according to the 30 disease and environment. -~
The disease control was recorded by the following grading~
', .
- 20 ~ 3 ,~
4 = no disease 3 = trace - 5% of disease on untreated plants .. 2 = 6-25~ of disease on untreated plants .~ 1 = 26-59% of disease on untreated plants 0 = 60-100% of disease on untreated plants The results are shown in Table II.
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Claims (31)
1. A compound of general formula (I) wherein R1 is an alkyl group containing from 1 to 6 carbon atoms, cycloalkyl containing up to 6 carbon atoms or phenyl optionally substituted with halogen, an alkyl group containing from 1 to 5 carbon atoms, an alkoxy group containing from 1 to 4 carbon atoms, trifluoromethyl, nitro or phenoxy; and R2 is phenyl or benzyl either optionally substituted with halogen, an alkyl group containing from 1 to 5 carbon atoms, an alkoxy group containing from 1 to 4 carbon atoms, trifluo-romethyl, nitro or phenoxy, or R2 is phenylphenyl when R1 is alkyl or cycloalkyl; and acid addition salts and metal complexes thereof
2. A compound according to Claim 1 characterised in that R1 is C1-4 alkyl and R2 is optionally substituted benzyl as defined in Claim 1.
3. A compound according to Claim 1 characterised in that R1 is optionally substituted phenyl as defined in Claim 1 and R2 is optionally substituted benzyl as defined in Claim 1.
4. A compound according to Claim 1 characterised in that each of R1 and R2, which may be the same or different, is optionally substituted phenyl as defined in Claim 1.
5. A compound according to Claim 1 characterised in that R1 is C1-4 alkyl and R2 is optionally substituted phenyl as defined in Claim 1.
6. A compound according to Claims 4 or 5 wherein the optionally substituted phenyl is 2,4-dichlorophenyl.
7. A compound according to Claims 1, 2 or 5 characterised in that R1 is butyl.
8. A compound according to Claims 1, 2 or 5 wherein R1 is t-butyl.
9. A compound according to any of Claims 1, 2 or 5 characterised in that R1 is n-butyl.
10. 1-(1,2,4-Triazol-1-yl)-2-(4-fluorophenyl)-2-(4-chlorophenyl)ethan-2-ol.
11. 1-(1,2,4-Triazol-1-yl)-2-(2-fluorophenyl)-2-(4-fluorophenyl)ethan-2-ol.
12. 1-(1,2,4-Triazol-1-yl)-2-(2-chlorobenzyl)-3-3-dimethyl-butan-2-ol.
13. 1-(1,2,4-Triazol-1-yl)-2,2-di(4-fluorophenyl)-ethan-2-ol.
14. 1-(1,2,4-Triazol-1-yl)-2-(4-chlorophenyl)-2-(2-chlorophenyl)ethan-2-ol.
15. 1-(1,2,4-Triazol-1-yl)-2-(4-fluorophenyl)-2-(2-chlorophenyl)ethan-2-ol.
16. A process for preparing a compound, salt or metal complex according to Claim 1, characterised by comprising reacting a compound of general formula (II) or (III) (II) (III) wherein R1 and R2 are as defined in Claim 1 without the proviso and X is halogen, with 1,2,4-triazole in the presence of an acid binding agent or with an alkali metal salt of 1,2,4-triazole in a solvent; and thereafter, if necessary, converting the compound into a salt or metal complex.
17. A process according to Claim 16 wherein a compound of formula II or III is brought into reaction with the sodium salt of 1,2,4-triazole at a temperature of from 20 to 100°C.
18. A process according to Claim 16 wherein the reaction is carried out using acetonitrile, methanol, ethanol or dimethylformamide as a solvent.
19. A process according to any of Claims 16, 17 or 18 wherein the compounds of general formula II and III are prepared by reacting a compound of general formula IVa or IVb (IVa) (IVb) wherein R1, R2 and X are as defined above with, respectively, a Grignard compound of general formula (Va) or (Vb):
Y-Mg-R2 Y-Mg-R1 (Va) (Vb) wherein R1 and R2 are as defined above and Y is a halogen in a convenient solvent.
Y-Mg-R2 Y-Mg-R1 (Va) (Vb) wherein R1 and R2 are as defined above and Y is a halogen in a convenient solvent.
20. A process according to any of Claims 16, 17 or 18 wherein the compounds of general. formula II and III are prepared by reacting a compound of general formula IVa or IVb (IVa) (IVb) wherein R1, R2 and X are as defined above with, respectively, a Grignard compound of general formula (Va) or (Vb):
Y-Mg-R2 Y-Mg-R
(Va) (Vb) wherein R1 and R2 are as defined above and Y is a halogen selected from the group consisting of chlorine, bromine and iodine, in a convenient solvent.
Y-Mg-R2 Y-Mg-R
(Va) (Vb) wherein R1 and R2 are as defined above and Y is a halogen selected from the group consisting of chlorine, bromine and iodine, in a convenient solvent.
21. A method of combating fungal diseases in a plant which method comprises applying to the plant, to seed of the plant or to the locus of the plant or seed a compound, salt or metal complex according to any of Claims 1, 2 or 3.
22. A method of combating fungal diseases in a plant which method comprises applying to the plant, to seed of the plant or to the locus of the plant or seed a compound, salt or metal complex according to any of Claims 4, 5 or 10.
23. A method of combating fungal diseases in a plant which method comprises applying to the plant, to seed of the plant or to the locus of the plant or seed a compound, salt or metal. complex according to any of Claims 11, 12 or 13.
24. A method of combating fungal diseases in a plant which method comprises applying to the plant, to seed of the plant or to the locus of the plant or seed a compound, salt or metal complex according to any of Claims 14 or 15.
25. A process for the preparation of a 1,1-diphenyl-2-(1,2,4-triazol-l-yl)ethanol of general formula I:
where one of the radicals R1, R2 and R3 is chlorine, and the others which may be identical or different, are hydrogen or chlorine, wherein a compound of the general formula II:
where R1, R2 and R3 have the meanings given for formula I and X is halogen, is reacted with 1,2,4-triazole, and thereafter, if necessary, converting the compound into an acid addition salt.
where one of the radicals R1, R2 and R3 is chlorine, and the others which may be identical or different, are hydrogen or chlorine, wherein a compound of the general formula II:
where R1, R2 and R3 have the meanings given for formula I and X is halogen, is reacted with 1,2,4-triazole, and thereafter, if necessary, converting the compound into an acid addition salt.
26. A 1,1-diphenyl-2-(1,2,4-triazol-1-yl)ethanol of general formula where one of the radicals R1, R2 and R3 is chlorine, and the others which may be identical or different are hydrogen or chlorine.
27. A process for the preparation of a 1-phenyl 1-alkyl-2-(1,2,4-triazol-1-yl)ethanol of general formula III
where R4 is alkyl of 1 to 4 carbon atoms and R5 is hydrogen or chlorine wherein a compound of the formula IV
is reacted with a 1,2,4-triazole of formula V
wherein X is an alkali metal in an inert organic solvent.
where R4 is alkyl of 1 to 4 carbon atoms and R5 is hydrogen or chlorine wherein a compound of the formula IV
is reacted with a 1,2,4-triazole of formula V
wherein X is an alkali metal in an inert organic solvent.
28. A compound of the formula III
where R4 is alkyl of 1 to 4 carbon atoms and R5 is hydrogen or chlorine.
where R4 is alkyl of 1 to 4 carbon atoms and R5 is hydrogen or chlorine.
29. A method of combatting fungal disease in a plant which method comprises applying to the plant, to seed of the plant or to the locus of the plant or reeda compound of formula III according to claim 27.
30. 1-n-Butyl-1-(4-chloro-phenyl)-2-(1,2,4-triazole-1-yl)-ethan-1-ol.
31. 1-Isobutyl-1-phenyl-2-(1,2,4-triazole-1-yl)-ethan-1-ol.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA000411715A CA1193274A (en) | 1979-03-07 | 1980-03-06 | Heterocyclic compounds |
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB7908003 | 1979-03-07 | ||
GB7908003 | 1979-03-07 | ||
GB7932819 | 1979-09-21 | ||
GB7932819 | 1979-09-21 | ||
AT0441880A AT371451B (en) | 1979-03-07 | 1980-09-02 | METHOD FOR PRODUCING NEW TIAZOLE COMPOUNDS AND THEIR ACID ADDITION SALTS AND METAL COMPLEXES |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA000411715A Division CA1193274A (en) | 1979-03-07 | 1980-03-06 | Heterocyclic compounds |
Publications (1)
Publication Number | Publication Date |
---|---|
CA1324146C true CA1324146C (en) | 1993-11-09 |
Family
ID=27149949
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA000347100A Expired - Lifetime CA1324146C (en) | 1979-03-07 | 1980-03-06 | Triazole compounds |
Country Status (3)
Country | Link |
---|---|
JP (1) | JPH0272130A (en) |
BR (1) | BR8001317A (en) |
CA (1) | CA1324146C (en) |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2623129C3 (en) * | 1976-05-22 | 1980-04-10 | Nordmark-Werke Gmbh, 2000 Hamburg | U-Diphenyl-3- (imidazol-1-yl) -propan-2-ols, process for their preparation and pharmaceuticals containing them |
US4413003A (en) * | 1977-07-29 | 1983-11-01 | Rohm And Haas Company | β-Hydroxyarylethylimidazoles |
-
1980
- 1980-03-05 BR BR8001317A patent/BR8001317A/en not_active IP Right Cessation
- 1980-03-06 CA CA000347100A patent/CA1324146C/en not_active Expired - Lifetime
-
1989
- 1989-07-19 JP JP1184861A patent/JPH0272130A/en active Pending
Also Published As
Publication number | Publication date |
---|---|
BR8001317A (en) | 1980-11-04 |
JPH0272130A (en) | 1990-03-12 |
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