Method of combating nematodes, and nematocidal preparations

3,178,338
United States Patent 0 "ice
Patented Apr. 13, 1965
l
_
_
_
2
following additives: Solvents with a boiling point of at
least 100° C., solidv carriers, dispersants, wetting or ad
3,178,338
METHOD OF COMBATING NEMATODES, AND
NEMATOCIDAL PREPARATIONS
hesive agents, fertilizers, and other pesticides.
Particularly valuable. preparations. for combating nema
todes—-more especially nematodes that cause damage in
Adolf Emil. .siegli?t, Basel, and. Rudolf Anliker, Biuningen,
Switzerland, assignors to Ciba Limited, Basel, Switzer
land, a company of Switzerland
‘
agriculture or horticulture-are those which contain as the
active principle a compound of the general, Formula 1 in
No Drawing. Filed Dec. 18, '1962, Ser. No. 245,433
Claims priority, application Switzerland, Dec. 28, 1961,
15,‘113/ 61
5 Claims. (Cl. 167-63)
The present invention provides nematooidal prepara
tions containing as active principle 1:13 :4~thiadiazo1e-thio
phene compounds of the general formula
(1)
‘which R1 represents a hydrogen atom or a methyl group
or the group
10
vin which X represents an oxygen or sulfur atom; R; stands
RFO‘—C_R3 S
15 tor a hydrogen atom, R3 for a hydrogen or chlorine atom
‘or a methyl group, and R4 represents a phenyl radical
which may be substituted by at- least one alkyl or alkoxy
group with l to 4 carbon atoms or by at least one chlorine
in which vR1 represents a hydrogen or chlorine atom, or
atom, or represents a, thienyl, furyl, pyridyl, diphenyl or
an alkyl group with l to. 4 carbon atoms, or the group
20 naphthyl' group.
'
Furthermore, there deserve spe'cialmentipn as the active
principle those of the general formula
HF-FH /S- HF-—~. CH
in which X is an oxygen or sulfur atom; R2 and R3 may
be identical or different and each represents a hydrogen 25
atom or an alkyl group with 1 to 4 carbon atoms, and R4
S
CH——.-CH
Hd\X/é—f|3N—-N
‘ \(?-—-(]J\s /d-.o/
\?—g \x'v/tlH
N——N
represents a mononuclear or binuclear aromatic radical
in which X stands for an oxygen or sulfur atom.
which may be substituted by one or several lower .alkyl
As examples of compounds of the general Formula 1
to be used according to
invention, there may be men
or alkoxy groups or halogen atoms, or a S-menrbered or
6-membered hetero‘cyclic radical and at least one of the 30 rtioned the compounds listed in the following ‘Table 1:
Table 1
Anal sis molecular weight
N0,
Formula
Properties
..
y .
(
Qalculated
1 _______ -_ H.C—OH
[1
HC,_CH
/ \
n'
C—~C
\ /
C-C
II
S
2 _______ __ H
S,
n
H0
I!
needles, M.P., 1512-15187 0. - H, 2.42 ______ ._ H, 2.724.
.(ethan'ol).
5., 38-42-------- S, 33-34
>
S
Colorless, very ?ne needles
M.P.,168.6-:=169.2° c.
I . Cl
H
S
HC_CH
n
/ \
S
?—0\ /C—€[)
I]
S
u
("3—C\ /GH
N———N
‘
?-e
N_N
CH3
____
OH;
/ \
>
HO\ /CH— H —— H-
N, 10.05; ____ _. N, 10.03.
278.79
Yellow shiny, ?ne ?akes,
C 46.
'
)
_____ __
|
_ (ll-CH3
CH:
____.
C, 45.85.
memiig above 300° 0. (ortho-
H’, 1.94
dichlorobenzene).
N,
13.
N,3829.
13.67.
S, 38.49__-__...
S,
S
H, 1.93.
($16.60)
C, 60., _____ __ C, 60.57.
137.2-138" c. (e haploid-Water
11,3.90 ,
H, 3.93.
2:1).
N, 10.
N, 10.91.
2
( v58 6)
S
n
n
Pale-yellow, ?akes, M.P.,
/ \
5 _______ ._ HC—— H
[[
HC——-CH
S
HC\ /C——(“3
S
S
/ \
'
C, 51161.
H’, 2.53 ______ __ H, 2.34.
( '
u
N———N
4 _______ _- HC—————CH
H
‘
u
HO\ /C~%I)
’
(dioxane+wa_ter 2:1).
~
'
(250.37)
0 51.70 _____ __
.
N.——-N
3 _______ _- HC——CH
N', 11.19 ..... -. N, 11.30.
S
—
S
C, 47:97-_____ .. C, 47.92.
n
H
11
/ \_ _/
HC\ /C+~(“J
("3
g.
a
Eound
CH
\ /
N-
——CH
Lightyyellow, ?ne, shiny
.
Colorless, felted needles,M.P.,
"
0, 62,96_
0, 63,71.
109.4—110° C. '(ethanQl-l-water
H, 5,37-
H, 54s
4:1).
N’, 955%.;
(
' )
5
N, 9.20.
CH3
6 _______ __ HC———
|[
H0
S
||
I
Colorless, shiny ?akes, M.P.,
/ \
C—0
\ /
II
N
C, 61.96.
1701-1112" 0. (ethanol+
C
11
N
,
.
CH;
water 3:1).
. H, 4.40.
'
N, 10.14.
,
Cl
7 _______ _. HC———CH
11
S
u
|
Colorless, shiny needles, M.P.,
/ \
122.2-122.s° 0. (ethanol).
HC\ S /o-<l? —N("1
0, 51,70 _____ _. C, 51.82.
H, 2.53 ...... __ H, 2.39.
N, 13,053“--.
N, 9.80.
( , 8.7 )
Cl
8 _______ __
—
ll
HO
S
H
\ /
I
Colorless, very ?ne needles,
/ \
C—-—C
ll
C
1%
-—Cl
0, 46.01 _____ __
C, 46.41.
M.P., 179.5?180D 0. (ethanol
11, 1.93 ______ -. H, 1.88.
+Water 9:1).
N, 8.94 ______ .. N, 8.98.
(313-24)
)
3,178,338
Table 1-Continued
m
8
m
...m.
g
0F
0H
m
N
03l0
am
_
~
.
_
_
‘I04
GUNCNNsS0"OH
H
Hm
“mmw,M+hw?+wmWM+wé.27sM+MM+My;umm?Pmym
mmow
Hm
/mum
wHm
mmum
mm.»
VMW
mum
mwm
.m@
mwq“Mm
vMm
Km
ymm$0vmmm
£065mmrma?mm?EBw.‘5wwmhmm““mhawk.suwwgmHum)2%cb$3»CH0.53M00nuqob5H10dmmea,owaeow1.xe,m01r mmm
H
H
H
H
H
H
H
H
n
u
m
m
n
o.
n
u
n
u
n
n
u
u
.
Ccol"HNnoec
n
u
n
n
N
u
u
n
u
n
u
n
u
.
n
u
0“
n
u
n
n
n
n
n
u
n
u
mu
w“
m
~11
m
H
M
n
.19
n
n
n
"
u
n
u
n
u
n
n
n
/
\
/
\
/
mErumamMme.Emawmmm?Wm.M».+
ev11IO2\1((\1 .
3w
H
_
3
_
C
3C3_
Cl.CI:.uH1H
C
o
.l1I\
l/
/
\
wma,a.m.CHC0H0
CCICSHC0SI.1C0
_,
H
\
_
H
H
\
_
H
\
_
_
_
_
/S
a”
/s
H
w
m
i
/s
/
953%
“M.mawmin“
9
5
m
"D
u
“n,
n
h
M
m
m
H
RN.QHN1%mmH?mmmF
..h
we
.t
,0
.y
a
v9
.v71ye
1...y1
.15
3..6e
.or
.t.E
y6
\)e1
r2
P
.6
C
1_.
o0.Hcclclc
_
H
_
/
H
_
H
_
/
/
H
_
ma
.0.
u
mwlo‘
.P.
do.
0...are
0.
4
ru.
1°m
mm
M
.2:
m?
m5mum.5PM
Hmwm
“[email protected],.a:mmm
mmn.
M07mm
..lm
\u/“Hm
6L,1“mm
6%t.7Mwm
kmun
.mmm
Y(16mm»,
.my
smm
F.111
@1
MI
Q
Am
0Am
537.07.60wo
H I6
V\.
CNNa2CNNSaCHIN3S NS\
1C
1H
_
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a
NCIN0clNGINoIN 0|0
m
..azc
oEGENQHNo?NN,A
3,178,338
Table 1-Continued
Analysis (molecular weight)
No.
Formula
Properties
7
_
V
V
Calculated
OHa
l
22 ______ -_
0 CH3
———C
H
S
H
H3C-0
/C—.- H
S
l
/ \
HC_—C
II
II
HzC-O
S
S
n
needles, M.P., 1s2-1s2.5° o.
—-0 CH;
(dioxane+water 1:1).
'
HC.———-CH
/ \
C—-/
Pale-yellow, very ?ne, felted
t]?
—————N
(‘BBQ
23 ______ __
7
Found
ll
Pale-yellow, ?ne crystalline
1]
powder, M.P., 142.8-144.2°
0-0
CH
n
\ /
——N
C. (methanol-l-water 2:1).
>
0
0 CH3
24 ______ __ HC—-—-
H
S
H
|
M.P., 158.8-159.1° 0. (ethanol
HC\ /C—(|%
S
25 ______ --
El]
N
CH
II
HO
H
Colorless, very ?ne needles,
/ \
is
H
H3C——O
S
Light-yellow, shiny needles,
(IJHa
II
H3C—C
S
. ., 163.2—165.2° o.
G
I!
(ethanol+water 2: 1).
~ N-f
V _——-—.N
H
/
S
II
II
———-N
(ethanol+water 1:2).
_N
HC—CH
/ \
I!
needles, M.P., 133.2—135° 0.
C
S
H
0-0
Pale-yellow, very ?ne, felted
/ \
C-C
28 ______ -_ HC——-—C
\O/
+water 1:1).
~-_-
/ \
C—C
H
M.1>., 134.94354‘1 0. (ethanol
0
[I
(3-0
/
ll
S
HG
+water 3:4).
N
—N
HC—.
2,7 ______ _-
——0 CH5
S
[I
C—0
\ /
[I
S
26 ______ __
Pale-yellow, very ?ne needles,
/ \
11
II
8
ll
C-0
\S/
HC_
/ \
C—0
i!
II
0-
11
OH
Yellow, ?ne, crystalline powder
_ .
.
(2
.
C, 49.98 _____ -_ C, 49.98.
[I
melting above 300° 0. (ortho-
n, 2.10 ______ __ H, 2.25.
CH
dichlorobenzene).
N, 1 .57 ..... __ N, 14.68.
\O/
The manufacture of the active principles of the general
Formula 1 incorporated with the agents of the invention
has been described in detail in British Patent No. 900.815,
granted October 31, 1962 to Ciba Limited.
(384.47)
acid, or of mixtures of these acids, or the sodium salt of
petroleum-sulfonic acid.
Suitable cationic dispersants are, for example, quater
nary ammonium compounds, such ascetyl pyridinium
The active principles of the general Formula 1 may be 45 bromide or dihydroxyethyldodecyl ammonium chloride.
For the manufacture of solutions for direct spraying
there may be further added organic solvents boiling
agents, by themselves or in admixture with the afore
used as solutions, emulsions or dispersions or as dusting
mentioned additives, for example in conjunction with fer
above 10Q° C. for example, mineral oil fractions, such
tilizers, ammonium salts, phosphates, calcium cyanarnide
as Diesel oil or kerosene, also coal tar oils and oils of
or urea, and also with pesticides, for example chlorinated 50 vegetable or animal origin, as well as hydrocarbons such
as alkylated naphthalenes or tetrahydronaphthalene, if
hydrocarbons, carbamates, thiocarbamates, phosphoric
acid esters and the like.
desired with concomitant use of mixtures of xylene, cyclo
The new agents may further contain identifying agents,
hexanols or kctones; also chlorinated hydrocarbons such
bactericides, fungicides and additional nematocides.
as tetrachloroethane, trichloroethylene or trichloroben
Aqueous sprays containing active principles of the
zenes or tctrachlorobcnzenes.
general Formula 1 may be prepared from emulsion con
centrates, pastes or wettable spray powders by the addi
For the manufacture of dusting or strewing materials
there may be used as solid vehicles talcum, kaolin, ben
tion of water, for example by grinding with sul?te cellu
tonite, calcium ‘carbonate, calcium phosphate or coal,
lose waste liquor. Further suitable emulsi?ers or dis
cork meal or wood meal or other materials, of vegetable
persants are non-ionic products, for example condensa 60 origin. It is very advantageous to prepare the materials
tion products of aliphatic alcohols, amines or carboxylic
in the form of granulates. The new products in their
acids containing a long-chain hydrocarbon radical con.
various forms of application may be admixed in known
taining about 10 to 30 carbon atoms with ethylene oxide,
manner with substances that improve the distribution,
such as the condensation product from octadecyl alcohol
adhesion, stability towards rain or the penetration power.
with 25 to 30 mols of ethylene oxide, or from soybean 65 As such substances there may be mentioned fatty acids,
fatty acid with 15 mols of ethylene oxide, or from soy
resins, glue, casein and alginatcs.
bean fatty acid with 30 mols of ethylene oxide, or from
The following examples illustrate the invention. The
commercial olcylamine with 15 mols of ethylene oxide,
parts are parts by weight.
or from dodecylmercaptan with 12 mols of ethylene oxide.
EXAMPLE 1
From among suitable anionic emulsi?ers there may be 70
mentioned: the sodium salt of dodecyl alcohol sulfuric
The compound shown under (1) in the above Table 1
acid ester, the sodium salt of dodecylbenzenesulfonic acid,
was mixed with aqueous sul?te cellulose waste liquor and
very ?nely ground. A series of dilution from 200 parts
the potassium or triethanolamine salt of oleic or abietic
3,178,338
.
7
8
per million downwards with the dilution factor 2 was
prepared by mixing the microdisperse preparation thus
consisting of the hydrogen atom, the chlorine atom, alkyl
containing 1 to 4 carbon atoms, and
obtained with water. 10 ml. each of the liquor were
dropped through a pipette into a Petri dish and 10 ml.
of a suspension of the nematodes Anguina tritici, Ditylen- 5
Hi
chus dipsaci and Heteroa'era schachtz'i respectively were
H
added. The Petri dishes were covered and kept for 6
days in di?use daylight. The broth was then ?ltered off,
FE /S\
~C
—
\X/
the ?lter residue rinsed with 1 liter of water and then
placed for 24 hours on a cotton wool ?lter infested with 10 in which X represents a member Selected from the group
nematodes. The surviving nematodes were able to work
their way through the ?lter and to collect in a pipette
and were then counted. The nematocidal effect achieved
is shown in the following Table 2:
consisting of the oxygen atom and the sulfur atom, R2
and R3 each represents a member selected from the group
consisting of the hydrogen atom and alkyl containing
1 to 4 carbon atoms, and R4 represents a member selected
Table 2
ACTIVE PRINCIPLE: 2:5-[DITHIENYL-(2’)]~1:3z4-THIADIAZOLE
Active principle in parts per
Control
million ...................... __ 100
50
25
12. 5
6. 25
3. 125
1. 6
0. 8
0. 0
It
Nematodes surviving after 6
ays:
Angui'na tritz'cz' _____________ __
Heterodera schachtii _________ -_
0
4
0
2
O
1D
1
13
0
4
0
3
0
27
0
18
356
110
from the group consisting of phenyl, a phenyl substituted
by at most 2 chlorine atoms, a phenyl substituted by at
most 2 alkyl containing at most 4 carbon atoms, a phenyl
EXAMPLE 2
substituted by methoxy, a phenyl substituted by methoxy
The test for nematocidal effects described in Example 30 and alkyl containing at most 4 carbon atoms, thienyl, di
1 was performed, using as active principle the compound
phenyl, naphthyl, pyridyl and furyl.
(2) in Table 1. The nematocidal e?ect thus achieved
2. A method as claimed in claim 1, wherein the objects
is shown in the following Table 3:
which are to be protected from the nematodes are treated
Good nematocidal effects were also achieved against
Ditylenchus dipsaci.
Table 3
ACTIVE PRINCIPLE: 2-[THIENYL-(2’)]-5-[4'-CHLOROPHENYL-(1')-1:3:4
THLADIAZOLE
Active principle in parts per
Control
million ______________________ __ 100
50
25
12. 5
6. 25
3. 125
1. 6
0. 8
0
0
13
0
0
0
0
0
0
O
0
0
0
0
0. 0
Nematodes surviving after 6
ays:
Anguina tritici _____________ --
0
0
Heterodera schachtz'i _________ -_
Good nematocidal e?ects were also achieved against
Ditylenchus dipsaci.
104
29
with a nematocidal amount of the compound of the
formula
EXAMPLE 3
nc—on
The test for nematocidal eifects described in Example 50
HQ)
1 was performed, using as active principle the compound
(3) in Table 1.
\
The nematocidal effect thus achieved is shown in the
following Table 4:
s
H -— a
ii-o/ \G-ii
"
lit
IH
/
3. A method as claimed in claim 1, wherein the objects
which are to be protected from the nematodes are treated
Table 4
Active principle in parts per
Control
million- _____________________ -_ 100
50
25
12.5
6. 25
3. 125
1. 6
0. 8
20
15
2
29
58
46
77
0.0
Nematodes surviving after 6
days: Anguina tritz'ci _________ _- 43
What is claimed is:
1. A method for combating nematodes which are harm
ful in agriculture and horticulture, wherein the objects
which are to be protected from the nematodes are treated
Wtih a nematocidal amount of a compound of the formula 70
Rr-
\ /
S
—G
C—R4
224
with a nematocidal amount of the compound of the
formula
HC_CH
S
at\S/LG/
\C@_a
l_l
II
II
N—"—N
4. A method as claimed in claim 1, wherein the 0b
in which R1 represents a member selected from the group 75 jects which are to be protected from the nematodes are
3,178,338
9
10
treated with a nematocidal amount of the compound of
in which X represents a member selected from the group
consisting of the oxygen atom and the sulfur atom, R2
and R3 each represents a member selected from the group
consisting of the hydrogen atom and alkyl containing 1
\ / _ii
s
to 4 carbon atoms, and R4 represents a member selected
u_
from the group consisting of phenyl, a phenyl substituted
by at most 2 chlorine atoms, a phenyl substituted by at
most 2 alkyl containing at most 4 carbon atoms, a phenyl
N———-—N
5. A composition for combating nematodes harmful in
agriculture and horticulture, which comprises a nema
substituted by methoxy, a phenyl substituted by methoXy
tocidal amount of a compound of the formula
10 and alkyl containing at most 4 carbon atoms, thienyl, di
phenyl, naphthyl, pyridyl and furyl, and in addition
thereto a member selected from the group consisting of
an organic solvent boiling above 100° C., water, a dispers
ing agent, a wetting agent and a solid carrier.
in which R1 represents a member selected from the group 15
References Cited by the Examiner
consisting of the hydrogen atom, the chlorine atom, alkyl
FOREIGN PATENTS
containing 1 to 4 carbon atoms, and
900,815
10/62 Great Britain.
20 JULIAN S. LEVI'IT, Primary Examiner.

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