IE43731B1 - A-(1,2,4-triazolyl or imidazolyl)-acetophenones and their use as pesticides - Google Patents
A-(1,2,4-triazolyl or imidazolyl)-acetophenones and their use as pesticidesInfo
- Publication number
- IE43731B1 IE43731B1 IE2173/76A IE217376A IE43731B1 IE 43731 B1 IE43731 B1 IE 43731B1 IE 2173/76 A IE2173/76 A IE 2173/76A IE 217376 A IE217376 A IE 217376A IE 43731 B1 IE43731 B1 IE 43731B1
- Authority
- IE
- Ireland
- Prior art keywords
- compound
- plant
- nitro
- halogen
- hydrogen
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
- C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
Abstract
Plant fungicidal compounds of formula: wherein y is -N- or -C(R)-, R, R1, and R2 are hydrogen, halogen, nitro or alkyl, R3 is hydrogen, furyl, thienyl or hydrocarbyl, R4 is hydrogen, halogen, nitro, phenyl, alkoxy or alkyl, n is 1 to 5, and z is C = 0 or a derivative thereof; and their salts.
Description
This invention relates to heterocyclic compounds which are imidazole or 1,2,4-triazole compounds, to a process for preparing them, to compositions containing them and to a method cf combating 'fungal pests using them.
The compounds have the general formula (X):-
wherein Y is =N- or =C(R)-, each of R, and R2 which may be the same or different, is hydrogen, halogen, nitro or alkyl (e.g. methyl, ethyl, propyl or butyl); R3 is hydrogen or furyl, thienyl or hydrocarbyl optionally substituted with halogen, acyloxy, cyano, hydroxy, nitro, alkoxy or unsubstituted or halo-substituted alkyl; R^ is hydrogen, halogen, nitro, phenyl, alkoxy or unsubstituted or halo-substituted alkyl; n is an integer of· 1 to 5, each of the R^ groups being the same or different when n is greater than 1; and Z is C = 0 or a functional derivative thereof (e.g. an imine, oxime, ketal, hydrazone or semicarbazone), or salts of said compounds.
The compounds form geometrical isomers. The invention includes within its scope such isomers each of which can be isolated from mixtures thereof by methods known in the art.
The term hydrocarbyl as used herein refers to monovalent organic radicals composed of hydrogen and carbon.
'-3731
The hydrocarbyl may be saturated or unsaturated, straight or branched chain or‘single ring; examples are alkyl, alkenyl, alkynyl, cycloalkyl,' aryl, aralkyl and alkaryl.
The hydrocarbyl is preferably C^_^, especially C^_g, hydrocarbyl, e.g. methyl, ethyl, propyl (n- or iso-propyl), butyl (η-, iso- or t-butyl), amyl, hexyl, heptyl, allyl, propynyl, phenyl, benzyl and substituted phenyl and benzyl. The alkoxy is suitably alkoxy, e.g. methoxy, ethoxy, propoxy or butoxy.
The halogen can be fluorine, chlorine, bromine or iodine. A suitably acyloxy group is acetoxy.
As indicated above, R^ can be substituted phenyl. Specific examples of such groups are 2-chloro- or fluorophenyl, 3-fluorophenyl, 4-fluoro-, chloro-, nitro-, nbutoxy-, methoxy-, cyano-, hydroxy- or acetoxy-phenyl, 2,4-, 3,4- or 2,6-dichlorophenyl, 2,4-dimethoxyphenyl or biphenyl.
Another suitable R3 group is trichloromethyl.
When R3 is thienyl or furyl, it is preferably 2-thienyl, 2-furyl or 5-chloro-2-thienyl.
When n is 1, R^ is preferably fluorine, chlorine or phenyl. When n is 2, the two R^ groups are preferably halogen, e.g. two chlorine atoms in 2- and 4-positions. A suitable halo-substituted alkyl is trifluoro- or trichloromethyl .
The salts can be salts with inorganic or organic acids, e.g. hydrochloric, nitric, sulphuric, acetic or oxalic acid.
63731
Examples of suitable triazole and imidazole compounds are given in, respectively, Tables I and II, wherein Z is
TABLE z
w
O O &
o oo z z
Η H >-3 M a o s ca
XP
W
CM
K □
z w
o o § 2 o
u in
O~ \ tn 0 W m vo £ υ
I xp
O {*» r-4 rH
U
I xp rH
I
KO co o
Γ
CM r-4
I in co
KO
O
CM
I σ» o
t xp o
KO r-1 r—1
I in (-4
CM CO i—4 I co CM r—1 xp r-4 r-4
I
CO υ
'
O
XP i—I r-4 I
CM i-4 o
r-4
I co σι σ» κο σν
CM r-4
I r*
CM r-4 υ u o
I I I
XT Xp Xj·
CO ffi
xp XP xp XI* r-4 KO K£ xp w W w W >1 a Xp U r- w Ό KO KO Ό rt i—4 1 w 1 w m KO in o U O U 0 >1 r-4 Ό o co . W υ W 1 | 1 •H h o U a) O KO 1 Ό CM o f**4 z Λ ΰ 1 1 S I CJ r-4 o o 0) U υ 4J •H Pm 1 ¢1 o w s 1 1 t 1 'ΰ 1 •fI 1 1 xp XP CM CM 1 xp T* XT xp XI* χί* 1 * XP CM
WWW
KWWWWWWWWWWffl o
rH
3731
EM Z w PS O 0 0 0 0 0 0 0 0 0 0 0 0 O ft CM σι cn r* 0 kO 0 CM xp in in i—1 kO k0 kO CM in ro in in o r* o H m XP Γ* CM rH r—1 pH rH t*- r—1 cn T—1 CM i-l r—i c—f rH I—1 CD CDO Ϊ 1 1 I s & o Γ- CM in xp xp co O ro xp ro O in H H kO CM in ro r* in co r~ o K in xp r* CM t) ih cM H H rH H r-1 CM rH «—1 fH j—1 rH 1-3 H B] O S ft rH r-1 «Η «—1 «-i r-1 H / xp fa u u o u o C.' υ ft Ρί w B B 1 1 1 B I I 1 1 I f S3 xp XP xP xp χρ Xp Xp Xp xp ro xp ro B XP B B k£> xp B xp xp kO kO XP xp CJ rH B kO 53« S3 E xp u u B B I > kO U B kO kO S3 1 I kO kO H £ O in 1 in kO U o kO >. »H o u CO a B o B o 1 I a X υ 1 1 C6 1 CM kO 0 kO 1 z K l 0 I rH in -H J2 o o n U fa u u ft -u •H o ffi *0 4J 1 I I 1 0 *ϋ I kO i β xp xp xp xp 0 1 xp o xp CM 1 nJ kO ·» xP | * CM xp CM CM P5 w B B B ffi B B B B X S3 E ffi B CM Pi s B b B B o B B S3 B B B s m z Q K o o Xp in kO Γ* co σ\ O H CM ro XP in 10 r- ft z 1—1 i—l rH H 1—1 I—1 CM CM CM CM CM CM CM CM s o a
S T 31
TABLE II
ο CU • s 120-122° 46-48° 115-117° 95-97° 143-145° 55-58° 130-132° .120-122° 154-156° 85-87° 147-149° 112-114° 109-110° 143-144° rM a pH rH pH pH *r a I Pm Pm I Pm I u a S3 a O O 1 S3 Pm 1 τρ tP «3· 4« τρ 4* τρ TP Tp TP 04 co CO CO CO a 33 a a VO Ό VO VO τρ τρ TP Tp τρ τρ tp tp Q I· a. Tp Tp υ u a a a a a a W S3 S3 a 1 VO VO VO VO VO VO VO VO pH H VO VO rH rH (J Q u U U □ <*) O | O O a u u I Ο I o 1 1 04 1 r-4 1 pH 1 Ol I pH I 04 pH •iH Td rH Ol •Η ♦h o ϋ o o u o o o Ό u O Ό Ό z 1 I 14 1 K I I | z 1 | 1 Tp 04 1 04 1 m3* VO VO τρ I τρ τρ τρ Tp Tp K s TP κ * 04 04 Ol Ol Ol pf Λ Q 33 S3 S3 a a a a a a a a a a a Ή § OUND 0 CO O pH Ol CO Tp in VO o- CO σ*ι o pH A z CM O| CO CO co co CO co co CO co fO τρ tP E O a
tab UK J. I CONTINUED
‘‘S'T3i
TABLE II CONTINUED
u ft a 0 XT O rd 1 CM o rd 76-78° 129-131° 126-128° 86-88° 150-152° 121-123° rd rd rd rd r-d U O o o u •rl •rl •H rd 43 rd Π3 *U U 04 u pi 1 1 K K M* •M· M1 3* *» K ·» s » CM CM CM CM CM CO *ro CO X ffi 1 ffi I 10 10 I CM 10 rd rd O u 1 o >1 >! £ I a 0 1 β β '0 in rd rd 10 id rd pH 0) Φ co u a Q ϋ u 0 >1 id o •rd -H Pi I 10 I 1 H C 04 XJ x; U rd •r-1 X! S) •rd 4J -P u τ) 1 0 -H a 1 1 1 43 CM CM CM •M* ip in -P ««3* *· co CM CM CM *-i K Q m K W ffi ffi W KJ M ffi *· PS c Ω S3 O O 0 Γ- co cn o rd CM CO M· in ΆΖ in LO in in 10 10 10 10 10 10 o o
It is believed that Compounds 1 to 22, 24 to 40, 43, 44 and 46 to 63 have the configuration (A), and that Compounds 23, 41, 42 and 45 are geometric isomers of Compounds 12, 33, 36 and 43, respectively, and it is believed that they have the configuration (B) .
The compounds of general formula (I) reacting a compound of general (II):may be made by
- 10 *37wherein Z, Y, R^, R2, R^ and n are as defined above, or a salt thereof, with an optionally substituted aldehyde of general formula R^CHO wherein is as defined above, using methods set out in the literature.
The reaction is suitably performed in the presence of a convenient base such as piperidine or pyridine in a high boiling hydrocarbon solvent e.g. toluene. Suitably a few drops of glacial acetic acid are present in the reaction mixture as a catalyst.
This process is generally performed ly refluxing the reactants together in a solvent and, after allowing reaction to occur, Isolating the product by removal of the solvent in vacuo. The product is then crystallised from a convenient solvent. In some cases both geometric isomers are formed in the reaction and these can be conveniently separated by chromatographic techniques. For example, the mixture of isomers can generally be chromatographed on silica as the stationary phase using a mixture of ethyl acetate/petroleum ether as the mobile eluent.
The acetophenone starting material of general formula (II) can be made by reacting an imidazole or triazole with the appropriate α-haloketone (e.g. an α-chloro or bromoketone) , using any of the methods set out in the literature. Usually the α-haloketone, in a convenient solvent (preferably acetonitrile or a hydroxylated solvent), is added to the imidazole or triazole in the same solvent at low temperatures.
- 11 4 3 7 31
The product can be isolated by removal of the solvent and extracting the residue into-an organic solvent with washing. Removal of the solvent gives the reguired compound which can be crystallised frgm a convenient solvent.
Alternatively, the compounds of general formula (I) can be made by dehydrogenating in known manner a compound of general formula (XXI):-
wherein η, Y, Z and R^ to R^ are as defined above, or a salt thereof. The dehydrogenation can be achieved for example by reaction with bromine in acetic acid followed by dehydrobromination, or directly by reaction with 2,3-dichloro-5,6dicyano-l,4-benzoguinone (DDQ).
/he compounds wherein Z is a derivative of C = 0 may be made from the'respective carbonyl compound using any of the standard technigues set out in the literature.
The compounds are active against a wide range of fungal diseases, particularly against the following:Puccinia recondita and other rusts on wheat and rusts on other hosts
Plasmopara viticola on vines
- 12 4 3 7 31
Erysiphe graminls (pbwdery mildew) on barley and wheat and other powdery mildews on various hosts such as
Sphaerotheca fullginea on cucumbers, Podosphaera leucotricha on apples and Unclnula necator on vines
Botrytis cinerea (grey mould) on tomatoes, strawberries, vines, and ether hosts
Pirlcularia oryzae on rice
Colletotrlchum lindemuthianum
Phytophthora infestans (late blight) on potato and tomato
Some of the compounds have also shown a broad range of 15 activities against fungi in vitro.
Further some of the compounds are active in ine form of seed dressings against Fusarlum spp., Septorla spp., Tllletla spp. and Pyrenophora spp. on cereals.
They also have certain plant growth regulating, herbi20 cidal, anti-bacterial, algicidal. and anti-viral activities.
The compounds may be used as such for anti-fungal purposes but are more conveniently formulated into compositions.
The invention therefore also provides a fungicidal 25 composition comprising, as an active ingredient, an imidazole
437 31 or triazole compound or salt thereof as defined above, and a carrier for the active ingredient.
The invention also provides a method for combating fungal diseases in a plant, which method comprises treating the plant, seed of the plant or the locus surrounding the plant or seed with an imidazole or triazole compound or salt thereof as hereinbefore defined.
The compounds can be used to combat plant pests and treat plants or seeds in a number of ways, for example they can be applied, formulated or unformulated, directly to the foliage of a plant which is infected or likely to become infected, or they can be applied also to bushes and trees, to seeds or to other medium in which plants, bushes or trees are growing or are to be planted, or they can be sprayed on, dusted on or applied as a cream or paste formulation. 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.
The term trieating as used herein refers to all these modes of application and the term plant includes seedlings, bushes and trees. Furthermore, the method of the invention includes preventative, protectant, prophylactic and eradicant treatment.
The compounds are preferably used for agricultural and horticultural purposes in the form of a composition. The
731 type of composition used in any instance will depend upon the particular purpose envisaged.
The compositions may be in the form of dusting powders or granules comprising the active ingredient and a solid diluent or carrier, for example, kaolin, bentonite, kieselguhr, dolomite, calcium carbonate, talc, powdered magnesia,
Fuller's earth, gypsum, Hewitt's earth, diatomaceous earth and China clay. Compositions for dressing seed, for example, may comprise an agent (for example a mineral oil) for assisting the adhesion of the composition to the seed.
The compositions may also be in the form of dispersible powders or grains comprising a wetting agent to facilitate the dispersion in liquids of the powder or grains which may contain also fillers and suspending agents.
The aqueous dispersions or emulsions may be prepared by dissolving the active ingredient(s) in an organic solvent optionally containing wetting, dispersing or emulsifying agent(s) and then adding the mixture to water which may also . contain wetting, dispersing or emulsifying agent(s).
* I
Suitable solvents are ethylene dichloride, isopropyl alcohol, propylene glycol, diacetone alcohol, toluene, kerosene, methylnaphthalene, the xylenes and trichloroethylene.
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.
By including suitable additives, for example additives for improving the distribution, adhesive power and resistance to rain on treated surfaces, the different compositions can be better adapted for various utilities.
The compounds can be used as mixtures with fertilisers (e.g. nitrogen - or phosphorus - containing fertilisers). Compositions comprising only granules of fertiliser incorporating, for example coated with, the triazole compound, are preferred. The invention therefore als>.. provides e fertiliser composition comprising the compound.
The compositions may also be in the form of liquid preparations for use as dips or sprays which are generally aqueous dispersions or emulsions containing the active ingredient in the presence of one or more wetting agent(s), dispersing agent(s), emulsifying agent(s) or suspending agent(s). These agents can be cationic, anionic or nonionic agents.
Suitable cationic agents are quaternary ammonium compounds for example, cetyltrimethylammonium bromide. Suitable anionic agents are soaps, salts of aliphatic monoesters of sulphuric acid (for example sodium laurvl sulphate), and salts of sulphonated aromatic compounds (for example sodium dodecylbenzenesuluhonate, sodium, calcium or ammonium lignosulphonate, butylnaphthalene sulphonate, and a mixture of sodium, diisoprooyl- end triisopropyl-naphthalene
4S73I sulphonates). Suitable non-ionic agents are the condensation products of ethylene oxide with fatty alcohols such as oleyl alcohol or cetyl alcohol, or with alkyl phenols such as octylphenol, nonylphenol 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 carboxymethylcel10 lulose), and the vegetable gums (for example gum acacia and gum tragacanth).
The compositions for use as aqueous dispersions or emulsions are generally supplied in the form of a concentrate containing a high proportion of the active ingredient(s), the concentrate to be diluted with water before use. These concentrates often should be able to withstand storage for prolonged periods and after such storage be capable of dilution with water in order to form aqueous preparations which remain homogeneous for a sufficient time to enable them to be applied by conventional spray equipment. The concentrates may conveniently contain 10-85%, generally 2560%, by weight of the active ingredient(s). When diluted to form 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 ingredient(s) may be used.
The compositions of this invention can comprise also other compound(s) having biological activity (e.g. growth stimulating substances such as the gibberellins), as well as stabilising agent(s), for example epoxides (e.g. epichlorhydrin).
The following Examples illustrate the invention; the temperatures are given in degrees Centigrade (°C).
EXAMPLE 1
1-(1,2,4-Triazol-l-yl.) -1-p-chlorophenacylstyrene (Compound 2)
Stage I. To aC-bromo-p-chloroacetophenone (4.64 g) in acetonitrile (50 ml) was added 1,2,4-triazole (1.4 g) followed by triethylamine (2 g). The mixture was stirred at room temperature for two hours and refluxed for one hour.
The solvent was removed under reduced pressure and to the residue water was added. The yellow solid which precipitated was filtered, washed with water and dried. Crystallisation from ethanol-petroleum ether (60-80°) gave 0C1,2,4-triazol-l-yl-o-chloroacetophenone as cream coloured plates, m.p. 148-150°.
3 7 31
Stage II. α-1,2,4-Triazole-l-yl-p-chloroacetophenone (3.35 g), benzaldehyde (1.59 g) and piperidine (6 drops) in toluene (30 ml) were refluxed in a azeotropic set up until no more water separated; this took about eight hours. The toluene was removed in vacuo and the residue was taken up in methylene chloride. The organic layer was washed with water, dried (MgSO4) and the solvent was removed. The residual oil solidified on cooling. Crystallisation from ethanol-petroleum ether (60-80°) gave the title compound as a yellow crystalline solid, m.p. 115-117°.
Compound 2 can also be made by the following procedure.
a-Benzyl-a-triazol-l-yl-p-chloroacetophenone (1.6 g) in acetic acid (15 ml) was treated with bromine (0.8 g) and the mixture was refluxed for six hours. Thin layer chromato15 graphy over silica gel showed that two component, were present in the reaction mixture and there was no change after further refluxing. Acetic acid was then evaporated off In vacuo. The residue was treated with water and was washed with water, sodium bicarbonate solution and water and was then dried (Na2S0^). The solvent was removed, and the residual oil was chromatographed over silica gel (60-120 mesh) eluting with petroleum ether (60-80°) ethyl acetate (1:1) to give, in low yield, the title compound as a pale yellow solid, m.p. 115-117°.
3 7 31
EXAMPLE 2
1-(1,2,4-Triazol-l-yl)-1-p-chlorophenacyl-p-fluorostyrene (Compounds 12 and 23)
OC-l,2,4-Triazol-l-yl~p-chloroacetophenone (25 g), pfluorobenzaldehyde (14.25 g), piperidine (10 drops) and acetic acid (20 drops) in toluene (200 ml) were refluxed in an azeotropic set up until no more water separated out; this took about two hours. Removal of toluene gave a yellow solid which was crystallised from ethyl acetate/petroleum ether (60-80°). One of the geometrical isomers of 1-(1,2,4triazol-l-yl)-1-p-chlorophenyl-p-fluorostyrene was obtained as a yellow crystalline solid, m.p. 167-169°. The other isomer was isolated from the filtrate by preparative thin layer chromatography on silica gel (Merck silica gel E-254) using ethyl acetate/petroleum ether (60-80°) (1-,1) as the eluent. Crystallisation from ethyl acetate/petroleum ether (60-80°) gave this isomer, m.p. 114-115°.
EXAMPLE 3
1-Imidazo1-1-yl-1-phenacy1-o-fluorostyrene (Compound 44)
Stage I. Phenacyl bromide (0.05 mol) and imidazole (0.02 mol) were stirred in methanol (50 ml) at 0° for 3 hours.
The methanol was removed in vacuo and the residue taken up in methylene chloride (300 ml), washed with water (3 x 100 ml), and dried (anhydrous sodium sulphate). Removal of the solvent left a solid residue which on recrystallisation from ethyl acetate gave 2-(imidazol-l-yl)-acetophenone (60%) as light brown needles, m.p. 112-113°.
Stage II. 2-(Imidazol-l-yl)-acetophenone (0.03 mol), 2fluorobenzaldehyde (0.03 mol), piperidine (2 drops), and glacial acetic acid (4 drops), were refluxed in toluene (25 mis) for 10 hours. The solvent was then removed in vacuo and the resultant brown solid washed with ethyl acetate/ petroleum ether. ,Recrystallisation from ethyl acetate gave 1-imidazol-l-yl-l-phenacy1-o-fluorostyrene as pale yellow crystals.
EXAMPLE 4
1- Imidazol-l-yl-l-phenacyl-p-nitrostyrene (Compounds 36 and 42)
2- (Imidazol-l-yl)-acetophenone (0.03 mol), 4-nitro benzaldehyde (0.03 mol), piperidine (2 drops), and glacial acetic acid (4 drops), were refluxed in toluene (50 ml) for 10 hours. The solvent was then removed in vacuo and the resultant brown solid purified by column chromatography on silica eluting with ethyl acetate/petroleum ether (7:3) to give Compound 42 as a pale yellow crystalline solid, m.p. 158-160° (ethyl acetate/petroleum ether), and Compound 36 as a pale yellow crystalline solid, m.p. 154-156° (ethyl acetate/petroleum ether).
EXAMPLE 5
The imidazole and triazole 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 Seed, as appropriate)- in 4 cm diameter mini-pots.
A layer of fine sand was placed at the bottom of the pot to facilitate uptake of test compound by the roots. Vermiculite was used to cover the seed in the soil tests.
The test compounds were formulated either by beadmilling with aqueous Dispersol T (Dispersol is a Registered Trade Mark) or as a solution in acetone/ethanol which was diluted to the required concentration immediately before use.
For the foliage diseases, 100 ppm a.i. suspensions were sprayed on to the foliage and applied to the roots of the same plant via the soil. (Sprays were applied to maximum retention, and root drenches to a final concentration eauivalent to approximately 40 ppm a.i./dry soil). Tween 20 (Tween is a Trade Mark), to give a final concentration of 0.1%, was added when the sprays were applied to the cereals.
For most of the tests, the test compound was applied to the soil and foliage one or two days before the olant was inoculated with the diseases. An exception was ι-he test on Erysiphe graminis, in which the plants were inoculated 24 hours before treatment. After 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 assessment varied from 4 to 14 days according to the disease and environment.
The disease control was recorded by the following grading:
= No disease = 0-5% = 6-25% = 26-60% = >60%
The results are shown in Table III.
3 7 3 1
TABLE III
DISEASE CONTROL 0 έ ft •Η tfl Μ W ω •rH β •rH 2 W in barley ^«ςρ^τΡτΡτΡτΤτρτρτΡτΤΠ in •H +1 W 4J 0 co (0 0 iH 0) β •Η □ in tomatoes τρ CO Ο · 1 Ο 1 ro 1 m m CM Ο Ο Ο CM CM (0 •H iH (0 rH β Q •H iH •rH cl Φ <0 Ν > Μ 0 in rice rH O CO Ο Ο I οοοοοοο ο nJ u <0 CL 0 s in rH ft (0 r-{ σ ο •Η 4J •Η > in vines CO co ro ί 1 I 11 1 Ο Ο CM Η rM nJ iH - 0 Λ +» us ft 0 4J > Λ ft 01 β 10 4J οι ο in tomato (Ο rH CM cm t O 1 Ο 1 O to CM O cm O CM . O rH nJ M C Ή Ο 0 β ft ί0 +4 τί ϋ β 0 0 φ ίΗ in wheat CM CM COCO | COCO I CO CO CM rH Tp co rH *H ...
Q
Z
P o o gj Ί3
O o
h cm co tp in vo r- co σ\ Ο H cm rH rH r-t
31
TABLE III CONTINUED
DISEASE CONTROL i Erysiphe I graminis I in barley ^PrJ'^'O’*OO'M,’3'CM’3’f0 Botrytis 1 cinerea in tomatoes iHmtNOviOOvimOvtN iO •d d «J rd 3 0 id d •d & Φ d N ->1 d 0 in rice 1 1 IOOI 1 O cn Ο Μ 1 ffl d fO a i W <0 rd A 1 viticola I in vines ^cvjHcncnOcncMcnO^cn flj d 0 X 4-> XJ a 0 > XJ ft I infestans 1 in tomato OcnOOOOOO I O cm n CO •d C •d υ a 3 cu <ΰ 4-J •d Ό 3 0 0 Φ d in wheat
O a
□ o o ft z s o u «
rd
id o
CM
CM
CM m xr CM CM
3 7 31
D ω
ο κ
e<
ο υ
Η
Η
Η &3 til
Λ «ίϊ
DISEASE CONTROL I Erysiphe 1 ω •d C •d £ nJ d tn in barley m C4 m -tr rd i m m *«r d* ω •d 4-) > Μ 4-) 0 CQ 03 0 d GJ ti •d 0 in tomatoes Oinf>*dOdO<*)idf4^c*·) «5 •d d (ϋ id α 0 •d d •d 04 0 (β N d 0 8 •d d ti •d I » O O O 1 1 O oj O O Γ-i «J d 03 CU 01 £ ω ti id On ti id 0 0 •d +J •d > β •d OdidrO^OnCNOidrOCM ti d 0 32 4-) 32 W 0 44 >· Λ 04 (fl ti ti 4-) ω 0 44 ti •d in tomato mmOOOOOOONr-lr^ ti ♦d ti •d 0 0 ti 04 ti 4J •d Ό ti 0 0 GJ d 44 ti O 32 s 5 Ογωγωγωγωγωγωγωγωγωγωγω
Ω
Ο Ω Ω S
I ο
ο ιη <ν \ο
Ν
OJ co (Ν ζΛ cq
Ο
ΓΩ
ΓΩ
ΓΩ ιη ω
κο m
n 7 n 4
TABLE III CONTINUED
DISEASE CONTROL Erysiphe I 0} •H τ-i tr in barley COrOfOfOxpxpCMfOCNCOfOfO Botrytis 1 cinerea I in j tomatoes fO^xPxPfOCMCOrHO^fOfn nJ •H M (0 i-H 3 ϋ •rl •H CL oryzae in rice CO-’O I Plasmopara I I viticola I in vines (nO nJ M 0 £ +» 43 ft 0 4J 43 ft | infestans | in tomato m O ro CM O <-4 1 IO! 1 1 (tf Ή £ •H 0 0 fl CL rd 4J •rl a 0 a QJ in wheat ηθΜΜΜ<ηΟ<ηΗ(ησΐΓΠ
Q
Z □
O O 04 Z §
o co co σι co
O xp
CM
XI»
CO
Xp
XP
Xp in xp
KO χρ l> co xp XP
31
TABLE III CONTINUED
DISEASE CONTROL a) X3 a «Ρ 01 > P ω 1 graminis 1 in barley ¢00^000000-^00^^^^00 01 •P -P >1 P -P O ffl 3 QJ P O 3 *H a in tomatoes srr-iojmmdm'S'nHNO 3 •P P id r—i 3 Ό •P P •P Ph & 3 N P 0 QJ O P P s •P 0.0 OHO no oooo 3 P 3 Qj 0 £ 01 3 rp PU 3 ip 0 0 •P +> •P 01 QJ 3 •P > 3 P OO OHOOOOrHOOol Itf L 0 r* +> Λ 0. 0 +1 > J3 Λ I infestans 1 in tomato Ο .ΟΟοιΟΟΟνοιγ'ΙΜΗ nJ •P •P 0 0 3 & 3 •P •P 3 0 ϋ 0) P •P 3 QJ Λ 5 3 P *3· ro co oo on τρ co co p cm on
Q z
P o o PU Z s o o o
in cP m
m in in r* co σν O in in in
Claims (26)
1. A compound of general formula (1):Y—NΛΑ. CH wherein Y is =N- or =C(R)-, each of R, R^ and R^ , which 5 may be the same or different, is hydrogen, halogen, nitro or alkyl; is hydrogen or furyl, thienyl or hydrocarbyl optionally substituted wi’-.h halogen, acyloxy, cyano, hydroxy, nitro, alkoxy or unsubstituted or halosubstituted alkyl; is hydrogen, halogen, nitro, phenyl, 10 alkoxy or unsubstituted or halo-substituted alkyl; n is an integer of 1 to 5, each of the R^ groups being the same or different when n is greater than 1; and Z is C ~ 0 or a functional derivative thereof, or a salt of such a compound. 15
2. A compound according to Claim 1 wherein Y is =N-, R^ is hydrocarbyl optionally substituted with halogen, nitro or alkoxy, and R^ is hydrogen, halogen, nitro or alkoxy.
3. A compound according to Claim 1 wherein Y is =N-, R^ 2o is hydrocarbyl optionally substituted with halogen, acyloxy, cyano, hydroxy, nitro or alkoxy or R 3 is unsubstituted furyl or thienyl, and is hydrogen, halogen, nitro, phenyl or alkoxy.
4. A compound according to Claim 1 wherein Y is =C(R)-, R, R^ and R 2 are hydrogen, R^ is hydrogen, alkyl optionally substituted with halogen or R^ is phenyl or benzyl optionally substituted with halogen, alkyl or nitro, and is hydrogen, halogen, nitro, alkoxy or unsubstituted or halo-substituted alkyl.
5. A compound according to Claim 1 wherein Y is =N-, and R 3 is propyl, phenyl, fluorophenyl, chlorophenyl, nitrophenyl, methoxyphenyl, butoxyphenyl, cyanophenyl, hydroxyphenyl, aoetoxyphenyl, dichlorophenyl, dimethoxyphenyl, biphenyl, 2-thienyl or 2-furyl.
6. A compound according to Claim 5 wherein R^ is hydrogen, fluorine, chlorine or phenyl.
7. A compound according to Claim 1 which is any one of Compounds 1 to 7 of Table I hereinbefore.
8. A compound according to Claim 1 which is any one of Compounds 8 to 26 of Table I hereinbefore.
9. A compound according to Claim 1 which is Compound 27 of Table I hereinbefore. - 30 4 3 7 31
10. A compound according to Claim 1 wherein Y is =C(R)- and R 3 is propyl, phenyl, fluorophenyl, chlorophenyl, nitro phenyl, dichlorophenyl or chloro-2-thienyl.
11. A compound according to Claim 10 wherein n is 1 and R^ 5 is hydrogen, fluorine, chlorine or phenyl, or n is 2 and the R^ groups are chlorine.
12. A compound according to Claim 1 which is any one of compounds 28 to 48 of Table II hereinbefore.
13. A compound according to Claim 1 which is any one of 10 compounds 49 to 63 of Table II hereinbefore.
14. A process for preparing a compound according to any one of the preceding claims, the proct-us comprising (a) reacting a compound of general formula (II) :- 15. Wherein Z, Y, R x , R 2 , R 4 and n are as defined in Claim 1, or a salt thereof, with an aldehydr of general formula R^CHO wherein R 3 is as defined in Claim 1; or (b) dehydrogenating a compound of general formula (III):31 4 3 7 31 wherein Z, Y, R^, Rg, R^, R^ and n are as defined in Claim 1, or a salt thereof.
15. A process according to Claim 14 substantially as described in any one of Examples 1 to 4.
16. A compound of general formula (X) or a salt thereof prepared by a process according to Claim 14 or 15.
17. A fungicidal composition comprising, as active ingredient, a compound or salt according to any one of Claims 1, 5, 6, 9 to 11, 13 and 16, and a carrier for the active ingredient.
18. A fungicidal composition comprising, as active ingredient, a compound or salt according to Claim 2 or 7, and a carrier for the active ingredient.
19. A fungicidal composition comprising, as active ingredient, a compound or salt according to Claim 3 or 8, and a carrier for the active ingredient. - 32 4373 ί
20. A fungicidal composition comprising, as active ingredient, a compound or salt according to Claim 4 or 12, and a carrier for the active ingredient.
21. A fungicidal composition according to Claim 17 sub5 stantially as described herein.
22. A method of combating fungal diseases in a plant. The method comprising applying to the plant, to seed of the plant: or to the ?ocus of the plant or seed, a compound or salt according to any one of Claims 1, 5, 6, 9 to 10 11, 13 and 16.
23. A method of combating fungal diseases in a plant, the method comprising applying to the plant, to seed of the plant or to the locus of the plant or seed, a compound or salt according to Claim 2 or 7.
24. A method of combating fungal diseases in a plant, the method comprising applying to the plant, to seed of the plant or to the locus of the plant or seed, a compound or salt according to Claim 3 or 8. 3 i
25. A method of combating fungal diseases in a plant, the method comprising applying to the plant, to seed of the plant or to the locus of the plant or seed, a compound or salt according to Claim 4 or 12.
26. A method according to Claim 22 substantially as described herein.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB41449/75A GB1504352A (en) | 1975-10-09 | 1975-10-09 | Alpha-(1,2,4-triazolyl or imidazolyl)-acetophenones and their use as pesticides |
| GB1897276 | 1976-05-07 | ||
| GB3483676 | 1976-08-20 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| IE43731L IE43731L (en) | 1977-04-09 |
| IE43731B1 true IE43731B1 (en) | 1981-05-26 |
Family
ID=27257680
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| IE2173/76A IE43731B1 (en) | 1975-10-09 | 1976-10-01 | A-(1,2,4-triazolyl or imidazolyl)-acetophenones and their use as pesticides |
Country Status (10)
| Country | Link |
|---|---|
| JP (1) | JPS5248664A (en) |
| AU (1) | AU505178B2 (en) |
| CA (1) | CA1075244A (en) |
| DE (1) | DE2645617A1 (en) |
| FR (1) | FR2327242A1 (en) |
| IE (1) | IE43731B1 (en) |
| IL (1) | IL50609A0 (en) |
| IT (1) | IT1068467B (en) |
| NL (1) | NL7611147A (en) |
| NZ (1) | NZ182230A (en) |
Families Citing this family (29)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2757113A1 (en) * | 1977-12-21 | 1979-06-28 | Siegfried Ag | IMIDAZOLYL VINYL ETHER AND PROCESS FOR THEIR PRODUCTION |
| DE2839388A1 (en) * | 1978-09-11 | 1980-03-27 | Siegfried Ag | IMIDAZOLYLVINYLAETHER AND THEIR USE |
| JPS6053018B2 (en) * | 1977-09-07 | 1985-11-22 | 住友化学工業株式会社 | Azole compounds, their production methods, and fungicides comprising the compounds |
| EP0003884A3 (en) * | 1978-02-23 | 1979-09-19 | Imperial Chemical Industries Plc | Alpha-beta unsaturated ketone derivatives useful as herbicides |
| EP0009298A1 (en) * | 1978-07-27 | 1980-04-02 | Imperial Chemical Industries Plc | Heterocyclic compounds, processes for their preparation, pesticidal compositions containing them and methods of combating pests |
| DE2845293A1 (en) * | 1978-10-18 | 1980-05-08 | Basf Ag | ALPHA -AZOLYL- ALPHA -PHENYLESSIGAIC DERIVATIVES |
| US4486218A (en) * | 1979-02-16 | 1984-12-04 | Bayer Aktiengesellschaft | 1-Vinyltriazole compounds and plant growth and fungicidal compositions |
| DE2905981A1 (en) * | 1979-02-16 | 1980-10-30 | Bayer Ag | 1-ALLYLTRIAZOLE DERIVATIVES, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS A PLANT PROTECTION PRODUCT |
| EP0015387B1 (en) * | 1979-02-16 | 1983-01-12 | Bayer Ag | 1-vinyltriazole derivatives, process for their preparation and their use as growth regulating agents and fungicides |
| US4554007A (en) * | 1979-03-20 | 1985-11-19 | Sumitomo Chemical Company, Limited | Geometrical isomer of 1-substituted-1-triazolylstyrenes, and their production and use as fungicide, herbicide and/or plant growth regulant |
| FR2457858A1 (en) * | 1979-04-05 | 1980-12-26 | Sumitomo Chemical Co | Geometrical isomers of 1-phenyl-2-triazolyl-penten-3-ol - and ether(s), useful as fungicides, herbicides, growth regulators and antimycotics |
| DE2929602A1 (en) * | 1979-07-21 | 1981-02-12 | Bayer Ag | TRIAZOLYL-ALKEN DERIVATIVES, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS FUNGICIDES |
| DE3000643A1 (en) | 1980-01-10 | 1981-07-16 | Bayer Ag, 5090 Leverkusen | METHOD FOR PRODUCING AZOLYL VINYL KETONES |
| DE3019046A1 (en) * | 1980-05-19 | 1981-11-26 | Bayer Ag, 5090 Leverkusen | TRIAZOLYL VINYL KETONES AND CARBINOLS, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS FUNGICIDES |
| DE3019045A1 (en) | 1980-05-19 | 1981-11-26 | Bayer Ag, 5090 Leverkusen | SUBSTITUTED PHENYL-TRIAZOLYL-VINYLKETONE, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS FUNGICIDES |
| DE3175673D1 (en) * | 1980-11-19 | 1987-01-15 | Ici Plc | Triazole compounds, a process for preparing them, their use as plant fungicides and fungicidal compositions containing them |
| DE3044801A1 (en) * | 1980-11-28 | 1982-07-01 | Bayer Ag, 5090 Leverkusen | ANTIMICROBIAL AGENTS |
| DE3044802A1 (en) * | 1980-11-28 | 1982-07-01 | Bayer Ag, 5090 Leverkusen | SUBSTITUTED 1-PHENYL-2-TRIAZOLYL-1-PENTEN-3-OLE, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS PLANT GROWTH REGULATORS AND FUNGICIDES |
| AU544099B2 (en) * | 1980-12-15 | 1985-05-16 | Sumitomo Chemical Company, Limited | Triazolylpentenols |
| DE3103068A1 (en) * | 1981-01-30 | 1982-08-26 | Basf Ag, 6700 Ludwigshafen | VINYLAZOLE, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE IN FIGHTING FUNGI |
| DE3221700A1 (en) * | 1982-06-09 | 1983-12-15 | Bayer Ag, 5090 Leverkusen | PLANT GROWTH INHIBITING AGENTS |
| FR2541114B1 (en) * | 1983-02-23 | 1986-04-11 | Sanofi Sa | ANTIFUNGAL PHARMACEUTICAL COMPOSITIONS FOR ORAL USE CONTAINING OMOCONAZOLE |
| EP0117811A3 (en) * | 1983-02-23 | 1987-06-03 | Sanofi S.A. | Fungicidal pharmaceutical compositions for oral administration |
| JPS61280481A (en) * | 1985-05-18 | 1986-12-11 | Shikoku Chem Corp | Novel imidazole compound and production thereof |
| JPS6272674A (en) * | 1985-09-26 | 1987-04-03 | Shikoku Chem Corp | Novel imidazole compound and production thereof |
| JPS6417A (en) * | 1987-02-20 | 1989-01-05 | Shikoku Chem Corp | Chemotherapeutic agent composition |
| JPH01113386A (en) * | 1987-10-27 | 1989-05-02 | Shikoku Chem Corp | Novel triazole compound and production thereof |
| JPH0651698B2 (en) * | 1987-10-27 | 1994-07-06 | 四国化成工業株式会社 | Novel imidazole compound and antifungal agent containing the compound as an active ingredient |
| WO2009088070A1 (en) * | 2008-01-09 | 2009-07-16 | Kureha Corporation | (heterocyclic methyl)azolylmethylcyclopentanol derivative and intermediate thereof, process for production of the derivative, and agricultural or horticultural preparation and protective agent for industrial material each comprising the derivative |
-
1976
- 1976-10-01 IE IE2173/76A patent/IE43731B1/en unknown
- 1976-10-05 NZ NZ182230A patent/NZ182230A/en unknown
- 1976-10-07 IL IL50609A patent/IL50609A0/en unknown
- 1976-10-07 AU AU18445/76A patent/AU505178B2/en not_active Expired
- 1976-10-08 NL NL7611147A patent/NL7611147A/en not_active Application Discontinuation
- 1976-10-08 CA CA263,004A patent/CA1075244A/en not_active Expired
- 1976-10-08 JP JP51120468A patent/JPS5248664A/en active Pending
- 1976-10-08 IT IT28166/76A patent/IT1068467B/en active
- 1976-10-08 DE DE19762645617 patent/DE2645617A1/en not_active Withdrawn
- 1976-10-08 FR FR7630299A patent/FR2327242A1/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| NZ182230A (en) | 1978-06-20 |
| AU1844576A (en) | 1978-04-13 |
| IE43731L (en) | 1977-04-09 |
| FR2327242B1 (en) | 1980-04-30 |
| FR2327242A1 (en) | 1977-05-06 |
| IT1068467B (en) | 1985-03-21 |
| NL7611147A (en) | 1977-04-13 |
| JPS5248664A (en) | 1977-04-18 |
| IL50609A0 (en) | 1976-12-31 |
| AU505178B2 (en) | 1979-11-08 |
| CA1075244A (en) | 1980-04-08 |
| DE2645617A1 (en) | 1977-04-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| IE43731B1 (en) | A-(1,2,4-triazolyl or imidazolyl)-acetophenones and their use as pesticides | |
| US4086351A (en) | 1,2,4-Triazole-containing compounds and their use as pesticides | |
| US4315016A (en) | Heterocyclic triazolylethyl ether compounds and their use as pesticides | |
| US4620011A (en) | Triazolyl ethanol derivatives | |
| US4079143A (en) | Fungicidal 1H-1,2,4-triazoles | |
| KR100271930B1 (en) | Azolylmethyl-fulurocyclopropyl derivatives | |
| CA1280417C (en) | Fungicidal acrylates and preparation thereof | |
| US4518600A (en) | Combating fungi with 1-phenoxy-2-pyrimidinyl alkanols | |
| KR900005696B1 (en) | Process for preparing substituted 1- hydroxyethyltriazolyl derivatives | |
| JPH0415226B2 (en) | ||
| IE43937B1 (en) | 1,2,4-triazole compounds and their use as pesticides | |
| JPH02188565A (en) | Propenoic acid derivative,preparation thereof, and fungicide,insecticide and tickicide composition containing same | |
| US4130409A (en) | Triazolyl butandiones | |
| US4325966A (en) | Fungicidal compounds, compositions and processes | |
| US4205075A (en) | Processes and composition for combating fungi | |
| US4394380A (en) | 2-(2-Alkoxyalkyl)-1,2,4-triazole compounds and their use as fungicides | |
| EP0304171B1 (en) | Pyrimidine derivatives | |
| US4067989A (en) | 1,3-Diazole heterocyclic compounds and their use as pesticides | |
| US4147793A (en) | Fungicidal azolyl-substituted aryl aralkylketone compounds | |
| CA1101428A (en) | Triazole and imidazole compounds and their use as fungicides and plant growth regulating agents | |
| NZ199985A (en) | Antimicrobial triazole derivatives | |
| HU205536B (en) | Fungicidal composition comprising substituted dioxolane derivatives and process for producing such compounds | |
| JP2825534B2 (en) | Fluorocyclopropyl derivative | |
| US4073925A (en) | Fungicidally effective imidazoles and use thereof against fungal pests | |
| JPS6140269A (en) | Azole compound and fungicide |