Note: Descriptions are shown in the official language in which they were submitted.
~136648
Case 136-6864
Canada
BROMOACETAMIDES
The invention relates to bromoacetamides possessing
fungicidal and bactericidal properties.
Accordingly, the present invention provides novel
bromoacetamides of formula I,
cH2\ R
I /CH - N - CO - CH2Br
wherein R is hydrogen, straight C2 4alkyl or branched
C4alkyl .
R is preferably hydrogen or n-propyl.
The present invention also provides a process for
producing a compound of formula I, which comprises
10 reacting a compound of formula II
CH
¦ ~CH - NH - R II
H2
wherein R is as defined above
with 2-bromo-acetylbromide.
The process of the invention may be carried out in a
manner known E~ se for the production of haloacetamides.
15It may e.g. be effected in an inert organic medium,
preferably in the presence of an acid acceptor, e.g. a
trialkyl amine such as triethylamine.
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The preparation of the compound of formula I
wherein R is hydrogen, hereinafter designated compound Iat
is preferably effec'~ed at reduced temperatures, especially
from about -10 to about +5C, preferably at about 0CC.
The preparation of the compounds of formula I
wherein R is not hydrogen (compounds Ib) is preferably
' effected at moderate ternperature, e.g. from about 15 to
35C, more preferably from about 20 to 2SC.
The reaction is preferably effected under essentially
10 anhydrous conditions. Suitable inert organic media include
halogenated hydrocarbons such as CH2C12 and, where any of
the reactants or the acid acceptor are liquid at the
reaction temperature, an excess thereof.
The compounds of formula I may be recovered and
15 refined by conventional means.
The compounds of formula II as well as 2-bromo-
acetylbromide are also known or may be prepared by
adapting procedures reported in the literature for the
preparation of their known analogs.
The compounds of formula I are indicated for
preventing or combatting fungi and bacteria in plants,
seeds or soil.
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The term "soil", as used herein is intended to embrace
any conventional growing medium, whether natural or
artificial.
The amount of compound of formula I to be applied to
5 attain the desired effect will, as will be appreciated,
depend on various factors such as the locus to be treated,e.g.
whether a plant, soil or seed treatment is envisaged, the
species of fungi or bacteria, mode of application, e.g.
whether the compound is applied as a foliar spray, a soil
10 treatment or a seed dressing, the conditions of the
treatment such as the time of application, whether the
treatment is prophylactic or therapeutic, the compound
employed and the like.
However, in general, satisfactory results are
15 obtained when the compound is applied to a locus, e.g.
on crops or to soil, at a rate of from about O.l to lO,
preferably about 0.2 to 5 kg (acti~Te ingredient)/hectare.
The treatment may be repeated as required, e.g. at 8 to 30
day intervals. When employed as a seed dressing,
20 satisfactory results are obtained when the compound-is
employed at a rate of from about 0.05 to 0.5, preferably
about O.l to 0.3 g/kg seed.
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Fungi against which compounds I are particularly
effective include those of the genus Fusarium sPP ., e.g.
F.o~ysporum f.s~ copersici in tomato
F.oxvsporum f.sp.vasjnfectum in cotton
F.oxysporum f.sp.cubense in banana
F.solani in vegetables
F.culmorum in cereals
F.graminearum in cereals
Verticillium ~., e.g. V. albo-atrum in a wide s~ectrum of
10 economically important crops such as cotton, hop, aifalfa
and solanaceous crops; V.theobromae in banana;
ColletotriChum spp., e.g. C.lindemuthian~ in beans;
-
Phytophthora s~., e.g. Ph.cactorum, Ph.~arasitica, andPh.cinnamomi. in susceptible plants;
15 Pythium spP., e.g. P.aphanidermatum in sugar beet;
Thielaviopsis basicola on a wide spectrum of crops;
Stereum spp., e.g. Stereum pur~ureum in pip and stone
fruit trees; of the
Order Ustilaginales, e.g. U.maYdis in corn;
Venturia spp., e.g. V. inaequalis in apples;
Phoma ~., e.g. Ph.betae on sugar beet; and
Pyricularia spp., e.g. P.oryzae on rice.
Bacteria against which compounds I are particularly
effective include those of the genus
~} ~
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Xanthomonas spp., e.g. X.malvacearum in cotton,
X.pelargonii in Pelargonium; and Pseudomonas spp., e.g.
P.tomato in tomato, P.syringae in susceptible plants.
Fungi and bacteria of the aforementioned genera
cause considerable damage in agriculture, e.g. in tomato,
cotton and cereal crops as well as in arboriculture and
ornamentals, and are difficult to prevent or combat.
The compounds of the formula I are especially useful
against Fusarium, Phytophthora, Ustilaginales, Pythium,
Colletotrichum, Stereum, Thielaviopsis, Verticillium,
Phoma, Venturia, Pyricularia, Pseudomonas and Xanthomonas.
The compounds may be employed as fungicidal and
bactericidal composition comprising a compound of
formula I and an inert fungicide or bactericide carrier.
In general, such compositions contain from about
0.01 to 90%, preferably from about 0.1 to 60% by weight
of active agent. They may be in concentrate form, for
dilution down prior to application, or in dilute, ready
to apply form. As examples of particular forms may be
given wettable powder, emulsion concentrate, dusting,
spraying, granulate and delayed release forms, incorpora-
ting conventional carriers and such other diluents and/or
adjuvants conventional in the agro-chemical art. Emulsion
concentrate forms generally contain from about 10 to 70~,
preferably about 20 to 60~ by weight of active ingredient.
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Solid, especially particulate compositions are preferred.
The compositions particularly adapted for spraying,
preferably include a surfactant such as a li~uid poly-
glycol ether, 2 fatty alkyl sulphate or a lignin sulphonate.
~oreover, further fungicides, bacteriaidal or other
beneficially-acting materials, such as insecticides, may
be present in the formulations and are contemplated as
urther e~bodiments of this invention.
- Concentrate forms of compositions for fungici~e use
10 genexally contain between about 2 and 80~, preferab].y
between about 5 and 70~, by weight of a compound of
formula I as active agent. Application forms of those
compositions generally contain between about 0.01 and 10~,
by weight of a compound of formula I as active agent.
The fungicidal/bactericidal activity of compounds
of formula I is indicated by conventional tests such as
described below:
~, , .
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Test method A: In vivo test employing Tomato ~ilt
(Fusarium ox~sporun f.s~. lycoPersici)
.
Lycopersicon esculentum cv. 'Rheinland's Ruhm'
(tomato) is cultivated in a mixture of peat and sand in
planter boxes for 10 days. Vapour-sterilized peat is
infested with Fusarium-inoculum and the mixture then
~ treated by a soil mix method to give concentrations of
160, 40 and 10 ppm of active ingredient per volume of
soil. After transfer of the treated, infested peat to
10 plastic pots of 6 cm diameter, the pots are planted with
tomato seedlings from ~he planter boxes. The plants are
- incubated at a temperature of 27C and G0-70% rH for 21
days. The efficacy of the active agent treatment is
determined by comparing the degree of wili (symptoms) with
15 that of untreated, similarly inoculated check plants.
In the case of each of the compounds of Examples 1
- to 3, particularly in the case of the compounds of
Examples 1 and 2, a fungicidal activity is observed.
An analogous test with simialr results is run on
20 Pythium aphanidermatum on cucumber and Phoma beta on sugar
beet.
Test method B: In vitro test employing
~aydis (corn smut).
,~ .
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Different concentrations of the active ingredient
are incorporated in malt agar plates to give concentrations
of 0.8 to 200 ppm a.i.. The plates are then inoculated
by spraying a spore suspension o~ U. maydis onto tllem or
placing an agar plug containing the fungus in the centre
of the plate. The plates are incuba~ed at room temperature
for 2-5 days. The efficacy of the active agent treatm~nt
is determined by comparing the growth of the fungus
with that in untreated, similarly inoculated plates.
In the case of each of the compounds of Examples 1 to
3, particularly in the case of the compounds of Examples 1
and 2, fungicidal activity is observed.
Analogous tests with similar results are run on the
follo~ing fungi/bacteria:
Venturia inaequalis, Pyricularia oryzae,
Phyto~hthora cactorum, Stereum purpureum,
Thielaviopsis basicola, Verticillium
albo-atrum, Co]letotrichum lindemuthianum,
Pseu~omonas tomato and Xanthomonas
_ . . ,
~elarqonii.
In addition to conventional carrier and surface-active
materials, formulations of the compound of formuia I of the
invention may also contain further additives with special
purposes e.g. stabilizers, deactivators (for solid formu-
25 lations on carriers with an active surface), agents for
lmproving the adhesion to plants, corrosion inhibitors,
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anti-foaming agents and colorants.
Examples of the produc~ion of fungicide and bacteria-
cides formulations are as follows:
a) Granulate
5 g of a compound of formula I e.g. 2-bromo-N-cyclo-
propyl-acetamide or 2-bromo-N-cyclopropyl-N-n-propyl-
acetamide are dissolved in 10 g of an aromatic solvent
preferably with a boiling point within the range of
135-213C. The solution is sprayed onto 90 g of crushed,
thoroughly sieved pumice ~grain size 0.3 - 1 mm) by a
conventional technique.
b) Emulsion - Concentrate
25 Parts by weight of a compound of formula I, e.g.
2-bromo-N-cyclopropyl-acetamide or 2-bromo-N-cyclopropyl-
N-n-propyl-acetamide are mixed with 30 parts by weight of
iso-octyl phenyl octaglycol ether and 45 parts by weight
of a petroleum fraction with a boiling range of 210-280C
(D2o:0.92). The concentrate is diluted with water to the
desired concentration.
c) Wettable Powder
-
50 Parts by weight of a compound of formula I, e.g.
2-bromo-N-cyclopropyl-acetamide or 2-bromo-N-cyclopropyl-
N-n-propyl-acetamide are mixed with 2 parts by weight of
sodium lauryl sulphate, 3 parts by weight of sodiu~
lignin sulphonate and 45 parts by weight of ~aolinite.
The concentrate can be diluted with water to the desired
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concentration.
d) Seed dressinq
45 Parts by weight of a compound of formula I, e.g.
2-bromo-N-cyclopropyl-acetamide or 2-bromo-N-cyclopropy]-
N-n-propyl-acetamide are mixed with 1.5 parts of diamyl-
phenoldecaglycolether ethylene oxide adduct, 2 parts ofspindle oil, 51 parts of fine talcum and 0.5 parts of
colorant rhodamin B. The mixture is ground in a contra-
plex mill at 10,000 rpm until an average particle size of
less than 20 microns is obtained. The resulting dry
10 seed dressing powder has good adherance and may be
applied to seeds, e.g. by mixing for 2 to 5 minutes in
a slowly turning vessel.
Other conventional forms such as paints useful in
treating plant wounds are also contemplated.
In the following examples, which are illustrative of
the invention, temperatures are in degrees in centigrade,
and room temperature is 20 to 30C, unless indicated
otherwise.
~13664,~
~ 136-6864
,
Example 1 : 2-Bro~o-N-cyclo~ro~yl-ac2tamide
6.92 ml (0.1 mol) of cyclopropylamine is mixed with
13.9 ml (0.1 mol) triethyl~mine in 250 ml of methylene
chloride and cooled to 0. 8.75 ml (0.1 mol) o 2-bromo-
acetylbromide dissolved in 50 ml of methylene chloride is
added dropwise, with stirring, over a period of 0.75 hou s,
maintaining the temperature at 0 with external coolins.
The mixture is allowed to come to room temperature and
stirred for an additional 18 hours. lhe reaction mixture
is then ~orked up by washing t~ice with 50 ml portions of
saturated aq. sodium bicarbonate solution, then 50 ml
of brine, drying over anhydrous sodium sulphate,
filtering and evaporating the filtrate in vacuo to obtain
a tan solid which upon recrystallizing from hexane-methy-
lene chloride (9:1) yields the title compound as a tan
solid, m.p. 114-116.
Example 2 : 2-Bromo-N-cyclo~ro~yl-N-n-~ro~yl-acetamide
6 g (0.06 mol) of N-cyclopropyl~n-propylamine and
6.12 g (8.6 ml; 0.06 mol) of triethylamine in about
,,~
.:
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150 ml of methylene chloride is placed in a vessel
equipped with a skirrer, a gas inlet and an addition
funnel. 12.3 g (5.3 ml); 0.06 mol) of ~-bromo-acetyl-
bromide in 20 ml of methylene chloride are added at 20 to
25 over a period of 40 min. under dry nitrogen gas with
stirring and stirring is continued for an additional hour.
The mixture is then washed 3 times with 30 ml portions of
10~ hydrochloric acid, 3 times with 30 ml portions of 10
aq. sodium bicarbonate solution and twice with 30 ~ll
10 portions of brine, dried over anh. magnesium sulphate,
and the solvent removed by evaporation to obtain crude
title product which is refined by distilling at 100 at
0.2 mm Hg using a kugelrohr apparatus.
N-Cyclopropyl-n-propylamine used as starting
15 material is obtained by reaction of cyclopropylamine with
propionyl chloride and reduction of the so obtained
N-cyclopropyl-propylamide (m.p. 39-41) with borane in
tetrahydrofuran.
Example 3
Following the procedure of Example 2, but in place
20 of the N-cyclopropyl-n-propylamine used therein,
using an approximately equivalent amount of
A~
.
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a~ N-cyclopropyl--ethylamine;
b) N-cyclopropyl-n-butylamine or
c) N-cyclopropyl-sec.butylamine
there is accordingly obtained, respectively:
a) 2-bromo-N-cyclopropyl-N-ethyl-acetamide;
b) 2-bromo-N-cyclopropyl-~-n-butyl-acetamide and
c) 2-bromo-N-cyclopropyl-N-sec.-butyl-acetamide.
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