This invention relates to a process for combating fungi and bacteria,
especially fungal and bacterial infections in plants; and to fungicidal and bactericidal
compositions useful in agriculture.
The invention provides a process for combating fungi and bacteria
which comprises applying to a plant to seed of a plant, or to the locus of the
plant or seed a thiophene derivative having the general formula (I) :
wherein R&sub1; and R&sub2; each represents a hydrogen atom or an alkyl group having
1 to 4 carbon atoms and X represents a methylene group or an oxygen atom, or an
acid addition salt thereof.
The alkyl groups may be straight or branched chain groups having
1 to 6, eg, 1 to 4, carbon atoms; examples are methyl, ethyl, propyl (n-
or iso- propyl) and butyl (n-, sec-, iso or
t-butyl) and methyl is especially preferred.
The salts can be salts with inorganic or organic acids eg, hydrochloric,
hydrobromic, nitric, sulphuric, oxalic, acetic, tartaric, 4-toluene-sulphonic or
Examples of active compounds for use in the invention process include
2-tert-butyl-5-[2-methyl-3- (3-methylpiperidino)propyl]thiopene, 2-tert-butyl-5-[2-methyl-3-(4-methylpiperidino)propyl]thiopene,
and their acid addition salts
The invention further provides a composition for combating fungi
and bacteria in agriculture which comprises as an active ingredient, a thiophene
derivative as defined in any of the preceding paragraphs.
The thiophene derivatives are readily manufactured by reduction of
the thienylketone compound (II) of general formula :
(where R&sub1; and R&sub2; represent a hydrogen atom or an alkyl group having 1
to 4 carbon atoms, respectively, X, a methylene group or an oxygen atoms) by the
Clemmensen technique [E.L. Martin; Organic Reactions Vol 1, 155 (1942)]. The said
Clemmensen reduction reaction normally takes place in hydrochloric acid as solvent
and the concentrations of the hydrochloric acid used are in the range of 5-35%,
preferably, 20-30%. The zinc amalgam used is preferably prepared before use, and
1-3 parts of zinc dust is used to one part of the raw material thienylketone compound
(II). The reaction is preferably carried out by stirring the mixture for 15 minutes
- 48 hours at ambient temperature or solvent reflux temperature. The addition
of 35% hydrochloric acid in about 1-5 portions at appropriate intervals is preferred.
The resultant thiopene derivative (I) can be isolated by the ordinary technique
and clean-up is achieved by vaccuum distillation, recrystallisation, chromatography
and other techniques. Where necessary, the free bases of the derivative can be
converted to acid addition salts by standard techniques.
The thienylketone compound (II) used as a starting material in the
reduction reaction is a new compound which can be prepared by, for example, the
Mannich reaction [F.F. Blicke; Organic Reactions Vol 1, 308 (1942)] :
(where R&sub1;, R&sub2; and X represent the same atoms or groups as described previously).
This reaction is preferably carried out by agitation and reflux of 2-tert-butyl-5-propionylthiopene
(II), 35% formaldehyde solution and the amine compound (IV) in ethanol for 1-10
hours following the ordinary technique for the Mannich reaction. The resultant
thienylketone compound (II) can be isolated and purified by the usual methods.
The fungicidal compositions of the invention are active against,
and therefore the invention process is useful in combating, the following diseases
Pucciniareconita, Pucciniastriiformis and other rusts
on wheat, Pucciniahordei, Pucciniastriiformis and
other rusts on barley, and rusts on other hosts eg, coffee, first trees especially
apples, vegetables and ornamental plants Erysiphegraminis (powdery
mildew) on barley and wheat and other powdery mildews on various hosts such as
Sphaerothecafuliginea on cucurbits (eg, cucumber), Podosphaeraleucotricha on apples and Uncinulanecator on vines
Helminthosporium spp. and Rhynchosporium spp. on cereals
Cercosporaarachidicola on peanuts and other Cercospora
on for example sugar beet, bananas and soya beans Botrytiscinerea
(grey mould) on tomatoes, strawberries, vines and other hosts Venturiainaequalis (scab) on apples.
Some of the compounds have also shown a broad range of activities
against fungi invitro. They have activity against various post-harvest
diseases on fruit (eg, Penicilliumdigatatum and italicum
on oranges and Gloeosporiummusarum 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. and Helminthosporium
spp. on cereals, Rhizoctoniasolani on cotton and Corticiumsasakii on rice.
The compounds can move acropetally in the plant tissue. Moreover,
the compounds can be volatile enough to be active in the vapour phase against fungi
on the plant.
They may also be useful as industrial (as opposed to agricultural)
fungicides, eg, in the prevention of fungal attack on wood, hides, leather and
especially paint films.
The compounds also display plant anti-bacterial activity, eg, against
the disease Xanthomonasoryzae
(bacterial blight of rice), and the
present invention therefore includes a process of treating plants to combat bacterial
The compounds may be used as such for fungicidal purposes but are
more conveniently formulated into compositions for such usage. The invention thus
provides a fungicidal or plant growth regulating composition comprising a compound
of general formula (I) as hereinbefore defined, or an acid addition salt thereof.
The compounds and their acid addition salts can be applied in a number
of ways, for example they can be applied, formulated or unformulated, directly
to the foliage of a plant, or they can be applied also to bushes and trees, to
seeds or to other media 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, or they can be applied as a vapour; or as slow release granules. 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; or to the soil generally, to paddy water or to hydroponic culture systems.
The invention compounds may also be injected into plants or trees and they may
also be sprayed onto vegetation using electrodynamic spraying techniques.
The term "plant" as used herein includes seedlings, bushes and trees.
Furthermore, the fungicidal 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 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 fillers
such as kaoline, bentonite, kieselguhr, dolomite, calcium carbonate, talc, powdered
magnesia, Fuller's earth, gypsum, Hewitt's earth, diatomaceous earth and China
clay. Such granules can be 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 agent (for example a mineral oil) for assisting the adhesion of
the composition to the seed; alternatively the active ingredient can be formulated
for seed dressing purposes using an organic solvent (for example N-methylpyrrolidone
The compositions may also be in the form of dispersible powders,
granules 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). Suitable organic solvents are ethylene
dichloride, isopropyl alcohol, propylene glycol, diacetone alcohol, toluene, kerosene,
methylnaphthalene, the xylenes, trichloroethylene, furfuryl alcohol, tetrahydrofurfuryl
alcohol, and glycol ethers (eg, 2-ethoxyethanol and 2-butoxyethanol).
The compositions to be used as sprays may also be in the form of
aerosols wherin the formulation is held in a container under pressure in the presence
of a propellant, eg, 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
Alternatively, the compounds may be used in a microencapsulated form.
They may also be formulated in biodegradable polymeric formulations to obtain a
slow, controlled release of the active substance.
By including suitable additives, for example additives for improving
the distrubution, 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 fertilizers (eg, nitrogen-,
potassium- or phosphorus-containing fertilizers). Compositions comprising only
granules of fertilizer incorporating, for example coated with, the compound are
preferred. Such granules suitable contian up to 25% by weight of the compound.
The invention therefore also provides a fertilizer composition comprising the
compound of general formula (I) or a salt or metal complex thereof.
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 surfactants eg, wetting agent(s),
dispersing agent(s), emulsifying agent(s) or suspending agent(s); or which are
spray formulations of the kind suitable for use in electrodynamic spraying techniques.
The foregoing agents can be cationic, anionic or non-ionic agents. Suitable cationic
agents are quaternary ammonium compounds, for example cetyltrimethyl-ammonium bromide.
Suitable anionic agents are soaps, salts or aliphatic monoesters
of sulphuric acid (for example sodium lauryl sulphate), 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).
Suitable non-ionic agents are the condensation products of ethylene
oxide with fatty alcohols such as olely 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 and 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).
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), and the concentrate is 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 and electrodynamic 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
(eg, alkaryl or aryl sulphonic acids such as xylenesulphonic acid or dodecyl benzenesulphonic
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 dilution 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, eg, compounds having similar or complementary fungicidal
or plant growth activity or compounds having plant growth regulating, herbicidal
or insecticidal activity.
The other fungicidal compound can be, for example, one which is capable
of combating ear diseases of cereals (eg, wheat) such as Septoria,
Gibberella and Helminthosporium spp., seed and soil borne diseases
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
effect on the fungicidal activity of the compound of general formula (I). Examples
of the other fungicidal compound are carbendazim, benomyl, thiophanate-methyl,
thiabendazole, fuberidazole, etridazole, dichlofluanid, cymoxanil, oxadixyl, ofurace,
metalaxyl, furalaxyl, benalaxyl, fosetyl-aluminium, fenarimol, iprodione, procymidione,
vinclozolin, penconazole, myclobutanil, R0151297, pyrazophos, ethirimol, ditalimfos,
tridemorph, triforine, nuarimol, triazbutyl, guazatine, triacetate salt of l,l′iminodi(octamethylene)-diguanidine,
propiconazole, prochloraz, flutriafol, hexaconazole ie. the chemical 1-(1,2,4-triazol-1-yl)-2(2,4-dichlorophenyl)hexan-2-ol,
DPX H6573(1-((bis-4-fluorophenyl)methylsilyl)methyl)lH-1,2,4-triazole, triadimefon,
triadimenol, diclobutrazol, fenpropimorph, fenpropidin, chlorozolinate, diniconazole,
imazalil, fenfuram, carboxin, oxycarboxin, methfuroxam, dodemorph, BAS 454, blasticidin
S, kasugamycin, edifenphos, kitazin P, cycloheximide, phthalide, probenazole, isoprothiolane,
tricyclazole, pyroquilon, 4-chloro-N-(cyano(ethoxy)methyl)benzamide, chlorbenzthiazone,
neoasozin, polyoxin D, validamycin A, mepronil, flutolanil, pencycuron, diclomezine,
phenazin oxide, nickel dimethyldithiocarbamate, techlofthalam, bitertanol, bupirimate,
etaconazole, streptomycin, cypofuram, biloxazol, quinomethionate, dimethirimol,
1-(2-cyano-2-methoxyimino-acetyl)-3-ethyl urea, fenapanil, tolclofosmethyl, pyroxyfur,
polyram, maneb, mancozeb, captafol, chlorothalonil, anilazine, thiram, captan,
folpet, zineb, propineb, sulphur, dinocap, binapacryl, nitrothalisopropyl, dodine,
dithianon, fentin hydroxide, fentin acetate, tecnazene, quintozene, dichloran,
copper containing compounds such as copper oxychloride, copper sulphate and Bordeaux
mixture, and organomercury compounds.
The compounds of general formula (I) can be mixed with soil, peat
or other rooting media for the protection of plants against seed-borne, soil-borne
or foliar fungal diseases.
Suitable insecticides which may be incorporated in the composition
of the invention include pirimicarb, dimethoate, demeton-s-methyl, formothion,
carbaryl, isoprocarb, XMC, BPMC, carbofuran, carbosulfan, diazinon, fenthion,
fenitrothion, phenthoate, chlorpyrifos, isoxathion, propaphos, monocrotophas, buprofezin,
ethroproxyfen and cycloprothrin.
Suitable growth regulating compounds are compounds which control
weeds or seedhead formation, or selectively control the growth of less desirable
plants (eg, grasses).
Examples of suitable plant growth regulating compounds for use with
the invention compounds are the gibberellins (eg, GA&sub3;, GA&sub4; or GA&sub7;),
the auxins (eg, indoleacetic acid, indolebutyric acid, naphthoxyacetic acid or
naphthylacetic acid), the cytokinins (eg, kinetin, diphenylurea, benzimidazole,
benzyladenine or benzylaminopurine), phenoxyacetic acids (eg, 2,4-D or MCPA),
substituted benzoic acids (eg, triiodobenzoic acid), morphactins (eg, chlorfluoroecol),
maleic hydrazide, glyphosate, glyphosine, long chain fatty alcohols and acids,
dikegulac, paclobutrazol, flurprimidol, fluoridamid, mefluidide, substituted quaternary
ammonium and phosphonium compounds (eg, chloromequat chlorphonium or mepiquatchloride),
ethephon, carbetamide, methyl-3,6-dichloroanisate, daminozide, asulam, abscisic
acid, isopyrimol, 1-(4-chlorophenyl)-4,6-dimethyl-2-oxo-1,2-dihydropyridine-3-carboxylic
acid, hydroxybenzonitriles (eg, bromoxynil), difenzoquat, benzoylprop-ethyl 3,6-dichloropicolinic
acid, fenpentezol, inabenfide, triapenthenol and tecnazene.
The following Examples illustrate the invention. Examples Nos. 1-7
and 1A to 7A illustrate the preparation of the active compounds used in the invention
compositions and process. Examples Nos 8-17 illustrate compositions according
to the invention. Example 18 illustrates the process of the invention.
A mixture of 2-tert-butyl-5-propionylthiophene (2.94g), 3,5-dimethylpiperidine
hydrochloride (3.34g), 35% formaldehyde solution in water (3.86g), ethanol (5ml)
and one drop of concentrated hydrochloric acid is refluxed with agitation for
six hours. After the completion of the reaction, the mixture is cooled with ice-cold
water, and the white solid material deposited is filtered off and washed with
small amounts of water. Recrystallisation of the resultant white solid material
from a hexane-acetone solution gives 2-tert-butyl-5-[3-(3,5-dimethylpiperidino)-2-methylpropionyl]thiophene
hydrochloride as white crystalline plates (3.84g) with melting point between 188
- 190°C (decomposition).
EXAMPLES 2 - 7
The compounds given in the following table (Table I) were obtained
by using the same procedures as given in Example 1 except that new starting materials
were used in Examples 2-7 instead of 3,5-dimethylpiperidine hydrochloride.
The major signals obtained in NMR and mass spectrometry of the compounds
of Examples 1 - 7 are shown in the following table (Table II).
The freshly prepared zinc amalgam (which is prepared by adding mercury
(II) chloride (0.21g) to a mixture of zinc dust (2.13g) and 25% hydrochloric acid
(4ml) while agitating the mixture and decanting off the supernatant when two layers
separated after a while) is admixed with 2-tert-butyl-5-[3-(3,5-dimethylpiperidino)-2-methylpropionyl]thiophene
hydrochloride (1.79g) obtained in Example 1 and 25% hydrochloric acid (8ml) and
then refluxed for 24 hours with agitation. During the course of the reaction,
35% hydrochloric acid (2ml) is added twice at 8-hour intervals. After completion
of the reaction, the reaction solution is diluted with water, alkalised by the
addition of caustic soda and subsequently extracted with benzene. The benzene layer
is washed with water, dried with anhydrous sodium sulphate and vaporisation of
benzene gives oily 2-tert-butyl-5-[3-(3,5dimethylpiperidino)-2-methylpropyl]-thiophene
(1.29g). The resultant oily substance is dissolved in carbon tetrachloride. Dry
hydrogen chloride gas is blown in. The deposited white solid is filtered off and
recrystallised from an acetone-hexane mixture to obtain 2-tert-butyl-5-[3,5-dimethylpiperidino)-2-methylpropyl]thiophene
hydrochloride as white crystalline plates with melting point in the 192-195°C range.
EXAMPLES 2A - 7A
The compounds given in the following table (Table III) were obtained
by using the same procedures as given in Example lA, except that new starting materials
were used in Examples 2A - 7A instead of 2-tert-butyl-5-[3(3,5-dimethylpiperidino)-2-methylpropionyl]thiophene
The major signals obtained in NMR and mass spedtrometry of the compounds
of Examples 1A - 7A are shown in the following table (Table IV).
An emulsifiable concentrate was made up by mixing the ingredients,
and stirring the mixture until all the constituents were dissolved.
Compound of Example 1      10%
Ethylene dichloride      40%
Calcium dodecylbenzenesulphate      5%
"Lubrol" L      10%
"Aromasol" H      35%
A composition in the form of grains readily dispersible in a liquid,
eg, water, was prepared by grinding together the first three ingredients in the
presence of added water and then mixing in the sodium acetate. The resultant mixture
was dried and passed through a British Standard mesh sieve, size 44-100, to obtain
the desired size of grains.
Compound of Example 2      50% "Dispersol"
"Lubrol" APN5      1.5%
Sodium acetate      23.5%
The ingredients were all ground together to produce a powder formulation
readily dispersible in liquids. Compound of Example 3      45%
"Dispersol" T      5%
"Lissapol" NX      0.5%
"Cellofas" B600      2%
Sodium acetate      47.5%
The active ingredient was dissolved in a solvent and the resultant
liquid was sprayed on to the granules of China clay. The solvent was then allowed
to evaporate to produce a granular composition.
Compound of Example 4      5%
China clay      95%
A composition suitable for use as a seed dressing was prepared by
mixing the three ingredients.
Compound of Example 5      50%
Mineral oil      2%
China clay      48%
A dusting powder was prepared by mixing the active ingredient with
Compound of Example 6      5%
A Col formulation was prepared by ball-milling the constituents set
out below and then forming an aqueous suspension of the ground mixture with water.
Compound of Example 7      40%
"Dispersol" T      10%
"Lubrol" APN5      1%
A dispersible powder formulation was made by mixing together the
ingredients set out below and then grinding the mixture until all were thoroughly
Compound of Example 1A      25%
"Aerosol" OT/B      2%
"Dispersol" A.C.      5%
China clay      28%
This Example illustrates the preparation of a dispersible powder
formulation. The ingredients were mixed and the mixture then ground in a comminution
mill. Compound of Example 2A      25%
"Perminal" BX      1%
"Dispersol" T      5%
China clay      34%
The ingredients set out below were formulated into a dispersible
powder by mixing then grinding the ingredients.
Compound of Example 3A      25%
"Aerosol" OT/B      2%
"Dispersol" A      5%
China clay      68%
In Examples 8 to 17 are the proportions of the ingredients given
are by weight.
The compounds set out in Examples 1 to 7 and 1A to 7A were all similarly
formulated as specifically described in Examples 8 to 17.
There now follows an explanation of the compositions or substances
represented by the various Trade Marks and Trade Names mentioned above.
LUBROL L : a condensate of nonyl phenol (1 mole) with ethylene oxide (13 moles)
AROMASOL H : a solvent mixture of alkylbenzenes
DISPERSOL T & AC : a mixture of sodium sulphate and a condensate of formaldehyde
with sodium naphthalene sulphonate
LUBROL APN5 : a condensate of nonyl phenol (1 mole) with naphthalene oxide (5.5
CELLOFAS B600 : a sodium carboxymethyl cellulose thickener
LISSAPOL NX : a condensate of nonyl phenol (1 mole) with ethylene oxide) (8 moles)
AEROSOL OT/B : dioctyl sodium sulphosuccinate
PERMINAL BX : a sodium alkyl naphthalene sulphonate
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). The test compounds were 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, the formulations (100 ppm active ingredient) were sprayed on to the
foliage and applied to the roots of the plants in the soil. 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 compound was applied to the soil (roots)
and to the foliage (by spraying) one or two days before the plant was inoculated
with the disease. An exception was the test on Erysiphegraminis
in which the plants were inoculated 24 hours before treatment. Foliar pathogens
were applied by spray as spore suspensions onto the leaves of test plants. After
inoculation, the plants were put into an appropriate environment to allow infection
to proceed and then incubated until the disease was ready for assessment. The
period between inoculation and assessment varied from four to fourteen days according
to the disease and environment.
The disease control was recorded by the following grading :
4 = no disease
3 = trace -5% of disease on untreated plants
2 = 6-25% of disease on untreated plants
1 = 26-95% of disease on untreated plants
0 = 60-100% of diseases on untreated plants
1. A method of combating fungi and bacteria, which comprises applying to a
plant, to seed of a plant, or to the locus of the plant or seed, a thiophene derivative
represented by general formula :
.wherein R&sub1; and R&sub2; each represents a hydrogen atom or an alkyl group
having 1 to 4 carbon atoms and X represents a methylene group or an oxygen atom,
or an acid addition salt thereof.
2. A method according to claim 1 wherein the thiophene derivative is 2-tert-butyl-5-(2-methyl-3-piperidinopropyl)thiophene.
3. A method according to claim 1 wherein the thiophene derivative is 2-tert-butyl-5-[2-methyl-3-(2-methylpiperidino)propyl]thiophene.
4. A method according to claim 1 wherein the thiophene derivative is 2-tert-butyl-5-[2-methyl-3-(3-methylpiperidino)propyl]thiophene.
5. A method according to claim 1 wherein the thiophene derivative is 2-tert-butyl-5-[2-methyl-3-(4-methylpiperidino)propyl]thiophene.
6. A method according to claim 1 wherein the thiopene derivative is 2-tert-butyl-5-[3-(3,5-dimethylpiperidino)-2-methylpropyl]thiophene.
7. A method according to claim 1 wherein the thiophene derivative is 2-tert-butyl-5-(2-methyl-3-morpholinopropyl)thiophene.
8. A method according to claim 1 wherein the thiophene derivative is 2-tert-butyl-5-[3-(2,6-dimethylmorpholino)-2-methylpropyl]thiophene.
9. A process for combating plant fungi which comprises applying to plants or
seeds, or to their locus.
10. An antifungal and antibacterial composition for use in agriculture comprising,
as an active ingredient, a thiophene derivative represented by general formula
wherein R&sub1; and R&sub2; each represents a hydrogen atom or an alkyl group having
1 to 4 carbon atoms and X represents a methylene group or an oxygen atom, or an
acid addition salt thereof.
11. An antifungal composition according to claim 10 wherein the active ingredient
12. An antifungal composition according to claim 10 wherein the active ingredient
13. An antifungal composition according to claim 10 wherein the active ingredient
14. An antifungal composition according to claim 10 wherein the active ingredient
15. An antifungal composition according to claim 10 wherein the active ingredient
16. An antifungal composition according to claim 10 wherein the active ingredient
17. An antifungal composition according to claim 10 wherein the active ingredient