Note: Descriptions are shown in the official language in which they were submitted.
3~
.
This invention relates to pyridyliminomethylbenzene derivatives and
acid-addition salts thereof, and to their preparation. This is a divisional
application for Canadian patent from Canadian Patent Application Serial No.
345,301 filed on February 8, 1980.
The invention provides a compound of general formula (II)
xl
- N = C /
)n ~ ~ ~ - ( )m (II~
N
or an acid addition salt thereof,
~herein Xl is halogen; m is 0, 1 or 2; Y is an alkyl, haloalkyl, alkoxy, halo-
alkoxy, halo, nitro, aryloxy, haloaryloxy, cyano or alko~ycarbonyl moiety;
n is 0, 1 or 2; and Z is an alkyl, alkoxy or halo moiety.
The invention also provides a process for making a compound of formula
(II) which comprises reacting a thionyl halide with an N-(3'-pyridyl)benzamide
of general formula ~V):
H 0
\ N _ C ~
(Z~n ~ ~ (Y)m
wherein m, n, Y and Z are defined as above.
The compo~mds of the invention are useful intermediates in the
preparation of related pyridyliminomethylbenzene derivatives and acid-addition
, ~
32
salts thereof, the latter derivatives being compounds of general formula:-
N = C
~ ~ ~ )m ~I)
wherein X is cyano, ethynyl, optionally-substituted alkyl, optionally substitu-
ted alkoxy, cycloalkoxy, alkenyloxy, alkynyloxy, aryloxy, haloaryloxy, alkoxy-
aryloxy, aralkyloxy, haloaralkyloxy, alkoxyaralkyloxy, optionally-substituted
alkylthio> cycloalkylthio, alkenylthio, alkynylthio, arylthio, haloarylthio,
alkoxyarylthio, aralkylthio, or a group of formula
R
-N
\R2
where Rl and R2 are independently selected from hydrogen and optionally-sub-
stitu~ed alkyl, or Rl and R2 together with the interjacent nitrogen atom form a
heterocyclic ring of from 5 to 7 ring atoms, one of which ring atoms may be a
further.heteroatom selected ~rom nitrogen, oxygen and sulphur; m is 0, 1 or 2;
Y is a hydrogen atom or an alkyl, haloalkyl, alkoxy, haloalkoxy, halo, nitro,
aryloxy, haloaryloxy, cyano or alkoxycarbonyl moiety; n is 0, 1 or 2; Z is an
alkyl, alkoxy or halo moiety; optional substituents being selected from halogen,alkoxy, aryloxy, alkylthio, arylthio, alkylamino, dialkylamino, alkalidenamino
and aryl moieties. ~It is noted that when n=0 then Z is a hydrogen atom).
The compounds of formula I are novel compounds and are the subject
matter of related Canadian Patent Application Serial No. 345,301. Such compoundshave been found to have fungicidal properties, and specific examples will be
-- 2 --
~ii63Z32
given hereinafter to illustrate the excellent activity of compounds of formula
I as fungicides and the versatility thereof in terms of the wide range of fungus
species which can be controlled by using such compounds.
Accordingly, Canadian Patent Application 345,301 further provides a
fungicidal composition comprising a compound of formula I as defined above ~or
an acid-addition salt thereof) in association with at least one inert carrier
therefor, and a method of making such a composition which comprises bringing a
compound of formula I as defined above (or an acid-addition salt thereof) into
association with at least one inert carrier therefor.
Further in accordance with the invention of Canadian Patent Application
345,301 there is provided a method of protecting a crop from fungal attack com-
prising treating crops subject to or subjected to fungal attackl seeds of such
crops or soil in which such crops are growing or are to be grown with a compound
of formula I ~or an acid-addition salt thereof) or a composition according to
that invention.
The defined pyridyliminomethylbenzene derivatives of formula I are,
of course, compounds capable of forming acid-addition salts, for example, salts
of hydrohalic acids, particularly of hydrochloric acid, or of sulphuric acid.
Such salts are, therefore, also novel compounds; and they are of interest as
having the fungicidal activity of the pyridyliminomethylben~ene derivatives
from which they are formed (in a manner well-known per se). It is also noted
in regard to such compounds that desirably they should be non-phytotoxic, which
can readily be determined by routine test, since normally this is a requirement
of fungicidal compositions.
Referring to the compounds of formula I, the optional substituents in
the optionally substituted alkyl, optionally-substituted alkoxy and optionally-
substituted alkylthio groups are preferably selected from halogen, alkoxy, aryl-
-
32
oxy, alkylthio, arylthio, alkylamino, dialkylamino, alkylidenamino and aryl
moieties.
Alkyl, alkenyl, alkynyl, cycloalkyl, alkoxyaryl, and aralkyl moieties
in the various substituents in formula I preferably contain up to 10 carbon
atoms. Preferred aryl groups are phenyl groups. The alkyl, alkenyl and alkynyl
groups may be straight-chain or branched groups.
Preferred halogen substituents are chlorine, fluorine and bromine atoms,
chlorine being particularly preferred.
At present, preferred compounds of formula I from the point of view of
utilising the fungicidal activity which has been found to arise from the presence
of the 3'-pyridyliminomethylbenzene structure which characterises the compounds
of formula I are the simpler ~overall molecular structure wise~ pyridylimino-
methylbenzene derivatives in which n=0. However, there is also provided those
additionally substituted pyridyliminomethylbenzene derivatives in which one or
two of the defined substituents Z are present, which can be used, as desired, as
fungicidally active compounds where, for example, particular characteristics, for
example, particular physical properties are sought. The fungicidal activity
achievable with the compounds of formula I, and particularly those in which n=0,
is especially advantageous being such as to enable those in the art readily to
formulate, on the basis of the result of standard biological and physical tests,
a range of fungicidal compositions having the characteristics required for parti-
cular end use applications, for example, either relatively broad or relatively
specific activity fungus speciewise, activity which is transmitted through plant
tissue ~i.e. is not confined to the surfaces tested), and, by simple variation
of the nature of the defined substituents, compositions in which the active com-
pound exhibits significant vapour pressure. Also, such compounds have the advan-
tage of being usable in combination with other known fungicides where it is de-
23~
sired to provide compositions exhibiting a particular spectrum and level of
activity.
When X is a group of formula -NRlR , wherein R and R together with
the interjacent carbon atom form aheterocyclic ring of from 5 to 7 ring atoms,
the ring is advantageously a piperidinyl, pyrrolidinyl, piperazinyl, morpholinyl
or thiamorpholinyl ring, a six-membered nitrogen-containing heterocyclic ring be-
ing preferred.
Preferred compounds are those wherein X is alkyl, alkoxy, aryloxy,
alkyloxyalkoxy, alkylthio, alkylamino, substituted alkylamino, for example, amino-
alkyl amino and alkoxy-alkylamino, or dialkylamino, m is 0, 1 or 2, Y is halogen
and n is 0. Advantageously X is alkoxy, aryloxy, alkylthio, mono-alkylamino, di-
alkylamino or a six-membered nitrogen-containing heterocyclic ring attached to
the carbon atom through its nitrogen atom; and preferably X is Cl 6 alkoxy, Cl 6
alkylthio or di~Cl 6 alkyl) amino. Advantageously (Y)m is a cyano, halo or
haloalkyl substituent, and in the case of a single such substituent it is prefer-
ably attached at the 4-position of the benzene ring. In such case a single halo
substituent is preferred, and tY)m is then preferably a 4-chloro-substituent as,
for example, in a preferred compound: 4-chloro-~3'-pyridyl) lmino-C-~isobutyl-
thio~ methylbenzene.
However, compounds in which ~Y)m represents di-halo substitution are
also particularly effective. In such case ~Y)m is preferably dichloro-, and
advan~ageously the chlorine atoms are in the 2,4- or 3,4-positions of the benzene
ring.
There are also provided processes for preparing the compounds of
formula I. The compounds of formula I wherein X is other than optionally-substi-
tuted alkyl are prepared by reac*ing a compound of the invention of general
formula:
-- 5 --
~L~L6~;~3Z
N = C /
~Z)n ~ ~ (Y)m ~II)
where m, n, Y and Z are all as defined above and Xl is halogen, wlth a compound
of formula
Q - X
where X is as defined above other than alkyl and Q is hydrogen or an alkali
metal atom, optionally in the presence of an acid acceptor. Xl is preferably a
cnlorine atom.
The intermediates of formula II are themselves provided as one aspect
of the invention. They are conveniently prepared by reacting a thionyl halide
1~ with the appropriate N-~3'-pyridyl) benzamide of general formula:
H O
\ N - C
~ m (V)
where m, n, Y and Z are as defined above.
The compounds of formula I wherein X is optionally-substituted alkyl
are prepared by reacting a 3-amino pyridine of general formula
NH2
~ )n ~ ~III)
where n and Z are as defined above, with a compound of general formula
23Z:
X - C - ~ (IV)
~Y)
where X is optionally-substituted alkyl.
Compounds of formula I in which X is optionally-substituted alkylthio,
cycloalkylthio, alkenylthio, alkynylthio, arylthio, haloarylthio, alkoxyarylthio
or aralkylthio can also be prepared by alkylation of the corresponding thio-
anilides.
As previously stated the salts of the novel compounds of formula I can
be prepared from such compounds by methods well-known per se. Accordingly, and
with the specific exemplification of the formation of the hydrochlorides herein-after, it is considered unnecessary to describe such methods in detail since
those in the art will be familiar with them.
A carrier in a composition bearing the active ingredient is any materi-
al with which the active ingredient is formulated to facilitate application to
the locus to be treated, which may for example be a plant, seed or soilj or to
facilitate storage, transport or handling. A carrier may be a solid or a liquid,
including a material which is normally gaseous but which has been compressed to
form a liquid, and any of the carriers normally used in formulating fungicidal
compositions may be used.
Suitable solid carriers include natural and synthetic clays and sili-
cates, for example natural silicas such as diatomaceous earths; magnesium sili-
cates, for example talcs; magnesium aluminium silicates, for example attapulgites
and vermiculites; aluminium silicates, for example kaolinites, montmorillonites
and micas; calcium carbonate; calcium sulphate; synthetic hydrated silicon oxides
and synthetic calcium or aluminium silicates; elements, for example carbon and
sulphur; natural and synthetic resins, for example coumarone resins, po]yvinyl
~6~;~32
chloride, and styrene polymers and copolymers; solid polychlorophenols; bitumen;
waxes, for example beeswax, paraffin wax, and chlorinated mineral waxes; and
solid fertilisers, for example superphosphates.
Suitable liquid carriers include water; alcohols, for example isopro-
panol and glycols; ketones, for example acetone, methyl ethyl ketone, methyl
isobutyl ketone and cyclohexanone; ethers; aromatic or araliphatic hydrocarbons,
for example benzene, toluene and xylene; petroleum fractions, for example kero-
sine and light mineral oils; chlorinated hydrocarbons, for example carbon tetra-
chloride, perchloroethylene and trichloroethane. Mixtures of different liquids
are often suitable.
Fungicidal compositions are often formulated and transported in a con-
centrated form which is subsequently diluted by the user before application.
The presence of small amounts of a carrier which is a surface-active agent facili-
tates this process of dilution. Thus preferably at least one carrier in a com-
position according to the invention is a surface-active agent. For example, a
composition may contain at least two carriers, at least one of which is a surface-
active agent.
A surface-active agent may be an emulsifying agent, a dispersing agent
or a wetting agent; it may be nonionic or ionic. Examples of suitable surface-
active agents include the sodium or calcium salts of polyacrylic acids and
lignin sulphonic acids; the condensation products of fatty acids or aliphatic
amines or amides containing at least 12 carbon atoms in the molecule with ethylene
oxide and/or propylene oxide; fatty acid esters of glycerol, sorbitan, sucrose or
pentaerythritol; condensates of these with ethylene oxide and/or propylene oxide;
condensation products of fatty alcohols or alkyl phenols, for example ~-octyl-
phenol or p-octylcresol, with ethylene oxide and/or propylene oxide; sulphates or
sulphates of these condensation products; alkali or alkaline earth metal salts,
3Z32
preferably sodium saltsJ of sulphuric or sulphonic acid esters containing at
least 10 carbon atoms in the molecule, for example sodium lauryl sulphate, sodium
secondary alkyl sulphatesJ sodium salts of sulphonated castor oil, and sodium
alkylaryl sulphonates such as sodium dodecylbenzene sulphonate; and polymers of
ethylene oxide and copolymers of ethylene oxide and propylene oxide.
The compositions may for example be formulated as wettable powders,
dusts, granules, solutions, emulsifiable concentrates, emulsions, suspension con-
centrates and aerosols. Wettable powders usually contain 25, 50 and 75% w of
active ingredient and usually contain, in addition to solid inert carrier, 3 - 10
% w of a dispersing agent and, where necessary, 0 - 10 % w of stabiliser(s) and/
or other additives such as penetrants or stickers. Dusts are usually formulated
as a dust concentrate having similar composition to that of a wettable powder
but without a dispersant, and are diluted in the field with further solid carrier
to give a composition usually containing 1/2 - 10 % w of active ingredient.
Granules are usually prepared to have a size between 10 and 100 BS mesh (1.676 -
0.152 mm), and may be manufactured by agglomeration or impregnation techniques.
Generally, granules will contain 1/2 - 25 % w active ingredient and 0 - 10 % of
additives such as stabilisers, slow release modifiers and binding agents. Emulsi-
fiable concentrates usually contain, in addition to a solvent and, when necessary,
co-solvent, 10 - 50 % w/v active ingredient, 2 - 20 % w/v emulsifiers and 0 - 20
% w/v of other additives such as stabilisers, penetrants and corrosion inhibitors.
Suspension concentrates are usually compounded so as to obtain a stable non-
sedimenting flowable product and usually contain 10 - 75 % w active ingredient~
0.5 - 15 % w of dispersing agents, 0.1 - 10 % w of suspending agents such as
protective colloids and thixotropic ag0nts, 0 - lO % w of other additives such
as deformers, corrosion inhibitors, stabilisers, penetrants and stickers, and
water or an organic liquid in which the active ingredient is substantially in-
23æ
soluble; certain organic solids or inorganic salts may be present dissolved inthe formulation to assist in preventing sedimentation or as antifree~e agents
for water.
Aqueous dispersions and emulsions, for example compositions obtained
by diluting a wettable powder or a concentrate according to the invention with
water, also lie within the scope of the present invention. The said emulsions
may be of the water-in-oil or of the oil-in-water type, and may have a thick
'mayonnaise' - like consistency.
In order to illustrate the fungicidal activity of the compounds the
examples given hereinafter of a wide range of compounds within formula I and
representative of the scope thereof include results obtained by subjecting these
compounds to a variety of tests representative of the spectrum of fungus species
against which fungicidal compositions are required for use. The following tests
were carried out:
- 10
~Z3~
(a) Activity against a~ple ~owdery mildew (PODOSPMAERA LEUCOTRICHA;P.l)
The test is a direct anti-sporulant one using a foliar
spray. The upper surfaces of leaves of whole apple seedlings are
inoculsted by spraying with an aqueous suspension containing 105
conidia/ml 2 days prior to treatment with the test compound. The
inoculated plants are immediately dried and kept at glasshouse
ambient temperatures and humidity prior to treatment. The plants
are sprayed at a dosage of 1 kilogram o~ active material per
hectare using a track sprayer. After drying the plants are
returned to a compartment at ambient temperature and humidity for
up to 9 days, followed by assessment. Assessment is based on the
percentage of the lea~ area covered by sporulation compsred with
that on leaves of control plants.
(b) Activity against vine dowr.y mildew (Plasmo~era viticola; Pv.t)
The test is a translaminar protectsnt one using a foliar
spray. The upper sur~aces of leaves of whcle vine plants are
sprayed at a dosage of 1 kilogrsm of active material per hectare
using a track sprayer. The lower surfaces of the leaves sre then
inoculsted, up to 6 hours after treatment with the test compound,
by spraying with an aqueous suspension containing 105 zoospro-
&ngia/ml. The inoculated plants are kept ~or 24 hours in a high
humidity compartment, 4 days at glasshouse ambient temperature
and humidity and then returned for a further 24 hours to high
humidity. Assessment is based on the percentage of the lea~ area
covered by sporulation compsred with that on control leaves.
(c) Activity against vine grey mould (Botrytis cinerea;B.c)
The test is a direct eradicant one using a foliar spray.
The under-surface of the detached vine leaves are inoculated by
pipetting ten large drops of an aqueous suspension contsining 5 x
105 conidià/ml on to them. The inoculated leaves are kept
uncovered o~ernight during which time the fungus has penetrated
the leaf and a visible necrotic lesion may be apparent where the
drop was ~ade. The in~ected regions are sprayed directly with a
dosage of 1 Xg of active material per hectare using a track
sprayer. When the spray has dried the leaves are covered with
23;2
-
petri dish lids and the disease allowed to develop under the
moist conditions. The extent of the necrotic lesion beyond the
original drop together T~Tith the dosage of sporulation is compared
with that on control lea~res.
(d) Activit~ a~ainst ~eanut leaf s~ot (Cercos~ora arachidicola;Ca)
The test is a direct eradicant one using a ~oliar spray.
'~he upper surfaces of the leaves of peanut plants (12-20 cms
high, in monopots) are inoculated by spraying with an aqueous
suspension containing 105 conidia/ml 40-43 hours prior to treat~ent
with the test compound. 'Lhe inoculated plarts are kept at high
humidity and then allowed to dry d~ing the interval between
inoculation and treatment by spraying at a dosase of 1 kg of
active material per hectare using a track sprayer. After spraying
the plants are moved to a humid compartment at 25-28 C for a
further period of up to 10 da~s. Assessment is based on a comparison
between the levels of disease on the treated and control plants.
(e) Activit~ against potato late blight (Phytophthora infestans~
'~he test measures the direct protectant activity of compounds
applied as a foliar spray. Tomato plants, Cultivar Ailsa Craig,
1-15 cms high, in monopots are used. 'rhe whole plant is sprayed
at a dosage of 1 kilogram of acti~re material per hectare using a
track sprayer. The plant is then inoculated up to 6 hours a~ter
treatment hTith the test compound, by spraying with an aqueous
suspension containing 5 x 103 zoozporangia/ml. The inoculated
plants are kept in hight humidity for 3 days. Assessment is
bases on comparison between the levels of disease on the treated
and control plants.
(f) Activit~ a~_irst barle~ owder~I mildew (~rysiphe ~raminis, E~.)
'~he test measures the direct anti-sporulant activity of
compounds applied as a foliar spray. For each compound about 40
barley seedlings were grown to the one-leaf stage in a plastic
pot of sterile potting compost. Inoculation was effected by
dusting the leaves ~ith conidia of Erysiphe graminis, spp. hordei.
24 ho~rs a~ter inoculation the seedlings were sprayed with a
solution o~ the compound in a mixture of acetone (50~), surfactant
- 12 -
.~;232
.
(0.04%) a~d water using a track sprayer. The rate of application
was equivalent to 1 kg of active material per hectare. First
assessment of disease was made 5 days after treatment, when the
overall level of sporulation on the treated plants were compared
with that on control plants.
The ext~nt of disease control achieved in such tests is
expressed &S a control rating according to criteria in which a
greater than 80% disease control is given the rating 2.
Specific examples of compounds in accordance uith the
invention are provided by the following examples, which are
provided as illustrative but in no way limitative examples.
Relevant data pertaining to each of these examples is given in
the apperded Tables I and II. These tables include illustrative~
but non-limitative, rating 2 results (where available) in the
range of tests described above. The nature and extent (test
spread-wise) of the results quoted demonstrates the ~ood ar.d
useful fungicidal activity attainable using compounds in accordance
with the invention.
Example 1 - 4-Chloro-(3'-pyridyl)imino-C-(isoPropoxy)meth~lbenzene
A stirred mixture of N-(3'-pyridyl)-4-chlorobenzamide (7 g,
0.03 mole) and thionyl chloride (22.5 ml) was heated under reflux
for two hours. ~xcess thionyl chloride was then removed in vacuo
and the residue, 4-chloro--(3'pyriayl)imino-C(chloro)-methylbenzene
hydrochloride, was suspended in dry dimethoYyethane (75 ml). A
solution formed by dissolving sodium (2.43 g, 0.105 mole) in dry
isopropanol (100 ml) was poured into the suspension and the
resulting mixture was stirred for one hour at room temperature
and then heated under re~lux for si~teen hours. The solvent
component of the mixture was removed in vacuo, and the residue
was treated with diethyl ether. The ethereal solution was washed
twice with water and then aried over anhydrous magnesium sulphate.
A~ter removal of the ether, the residue was su~jected to chro-
matography on a silica gel column, eluting with diethyl ether/
hexane (1:1). The title product was obtained as a colourless
solid (yield, 53%) m.p. 65-67C. (Ref: WL ~o. 81910)
~ l16~;Z3~
A greater than 80~ disease control was achieved in the ?v.t
test.
Exam~le 2 - 4-Chloro-(3'-Pyridyl)imino-C-(isoPro~ylthio)methylbenzene
A stirred mixture ol N-(3l-pyridyl)-4-chlorooenzamide (7 g,
0.03 mole) and thionyl chloride (22.5 ml) was heated under reflux
for two hours. Excess thionyl chloride was removed in vacuo, and
the residue, 4-chloro-(3'-pyridyl)imino-C-(chloro)me~hylbenzene
hydrochloride, was treated with dry pyridine (lO0 ml). Isopropyl
mercapt&n (4.56 g, o.o6 mole) was added and the mixture was
stirred and heated in an oil-bath at a temperature in the range
from lO0-ll0C for sixteen hours. The solvent and other volatile
components of the mixture were removed in vacuo, and the residue
was treated with diethyl ether. The ethereal solution was washed
three times with water and then dried over anhydrous magnesium
su_phate. After removal of the ether, the residue ~as subjected
to chromatography on a silica gel colu~n, eluting with diethyl
ether!hexane (l:l). The ti-~le product was obtained as a yellow
solid (yield, 70~) m.p. 55.5-57 C. (Re~ L No. 819633
A greater than 80% disease control was achieved in the E.g.
test.
E~amPle 3 - 4-Chloro-(3'-Pyridyl)imino-C-(di-n-butylamino)methylbenzene
A stirred mixture of N-(3'-pyridyl)-4-ch~orobenzamide (7 g,
.03 mole) and thionyl-chloride (22.5 ml) was heated under reflux
for two hours. Excess thionyl chloride was removed in vacuo and
the residue, 4-chloro-(3~-pyridyl)imino-c-tchloro)methylbenzene
hydrochloride, was suspended in dry dimethoxyethane (125 ml).
Dry di-n-butylamine (19.4 g, 0.15 mole) T~as added and the resulting
mixture was stirred at ambient temperature overnight. The solvent
component of the mixture was removed in vacuo, and the residue
was treated with diethyl ether. The ethereal solution was washed
twice with water and then dried o~er anhydrous magnesium sulphate.
After removal of the ether, the residue was subjected to chromato-
graphy on a silica gel column, eluting with diethyl e~her, and
again on a silica gel column, eluting with diethyl ether/methylene
dichloride (l:l). The title product was obtained as a viscous
, ~
23%
oil (yield 28%). (Ref: WL No. 83216)
A greater than ôO% was achieved in the E.g. test.
Analysis: c~lculated for N3ClC20H26 : C 69.9; H 7.6; N 12.2
found : C 69.9; H 8.1; N 12.0
Ex~m~le 4 - 4-chloro-t3'-~ridyl)iminomethylben~ene
A stirred mixture of 3-aminop~yridine (9.4 g, 0.1 mole) and
4-chlorobenzaldehyde (14.05 g, 0.1 mole) in toulene (100 ml) was
heated under reflux under a Dean and Star~ trap for two hours,
a~ter which time the theoretical amount of water (1.8 ml) had
collected. The reaction mixture was diluted with toluene (100
ml) and then dried over anhydrous magnesium sulphate. The solvent
component of the mixture was removed in vacuo, 40/60 petroleum
spirit was added to the residue, and the resulting solid material
was filtered off, washed with 40/60 petroleum spirit, and dried.
The solid material was recrystallised from cyclohexane (150 ml)
to give the title product (yield 75%) mp 80-82C. (Ref: WL ~o. 83421)
Exam~les 5 to 37
The compounds listed in Tables I and II were prepared by
similar methods to those described in Examples 1 to 4: -
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