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Патент USA US3090731

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Unite
3,92,?21
ttes
Patented May 21, 1963
1
2
approximately 100 nematodes were introduced
embryo tray of 4 by 4 cm. having a cavity of
Subsequently, the tray was closed by means of a
ground glass guard in such manner as to admit
into an
3.5 ccs.
roughly
a quan
tity of oxygen su?icient to prevent immobilisation of the
nematodes by lack of oxygen. By means of a binocular
the vitality of the nematodes was determined after 4, 24,
48 and 140 hours respectively.
3,99%,721
TIEADEAZGLE
Jan Hendrik Uhienbroek and Johan Dirk Biiloo, ‘Van
Houtenlaan, Wcesp, Netherlands, assignors to North
American Philips Qompany, Inc, New York, N.Y., a
corporation of Delaware
No Drawing. Filed Feb. 13, 1959, Ser. No. 792,953
Claims priority, application Netherlands Feb. 13, 1958
29 Claims. (Cl. 167—-33)
In this manner the lowestconcentration of active com
10 pound in the suspension used was determined, which
It is known that 1.2.4-thiadiazoles, in which both car
bon atoms of the ring carry monovalent organic radicals
resulted in 100% kill of the test specimen after 140 hours
linked through sulphur, might be used for combating
exposure.
The tests were carried out on larvae of Heterodera
noxious insects and larvae of them. These organic radi
rostochiensis lured for two days from their cysts, Dity
cals may be alkyl-, cycloalkyl-, aralkyl-, alkoxyalkyl-, 15 lenchus dipsaci and larvae of Anguina tritici (both speci
aryloxyalkyl-, carbethoxyalkyl- or hydroxyalkyl groups.
mens soaked for 17 hours from 'dry condition).
The results of these tests are listed in Table I, which
states the minimum lethal dosage of the investigated com
It has now been found that 1.2.4-thiadiazoles, in which
a. halogen atom is linked to one of the carbon atoms of
the ring are active against noxious organisms and in par
ticular have a nematocide effect.
pound, killing all the test specimens within 140 hours’
20 exposure.
The present invention relates to a method of produc
ing a means for combating noxious organisms and in par
ticular nematodes, characterized in that a compound of
The minimum lethal dosage stated is the con
centration of the active compound of the suspension used,
expressed in parts by weight of active compound per
million parts by weight of diluent (water).
the general formula:
TABLE I
Compound
Mimi‘
N
O—-Ol
in which Hlg represents a halogen atom and R1 represents 30'
alkyl-, cycloalkyl-, aryl- or aralkyl group, the aliphatic
Heterodera Ditylenchus Ang'uz'na
S
a phenyl group or a group R2.S—-, in which R2 represents
a whether or not substituted, saturated or unsaturated,
chain whether or not being interrupted by oxygen or sul
phur, is mixed with inert, solid or ?uid carriers, if de 35
sired with the addition of surface-active materials and/ or
Nematodes
rostochiensis
CH3.OH2.CH(CH3).S.
I1.C5H11.S ____________ _.
represents a chlorine atom and R2 represents an alkyl 40
group with 1 to 12 carbon atoms such as methyl-, ethyl-,
propyl-, isopropyl-, butyl-, isobutyl-, isoamyl-, hexyl- or
12
6
6
6
50
6
12
25
100
50
50
500
25
100
50
25
12
25
100
12
50
50
1,000
100
___
6
50
6
CH3.CH(CH:).CH2.CH2.S____
6
100
12
n. O 61113.8 ____________________ __
6
25
50
250
6
50
100
1,000
1, 000
4
3
12
50
100
500
15
25
25
12
12
12
1,000
1, 000
50
25
12
12
6
1, 000
6
1, 000
1, 000
50
.
octyl group or an oxygen interrupted alkyl group such
as an ethoxyethyl group or an unsaturated group, for
example an allyl group and further compounds, in which 45
R2 represents a phenyl-, 4-chlorophenyl-, 4-methylphenyl
.
group or a benzyl- or 4-chlorobenzyl group or a phe
tritici
R1:
dispersion agents.
A satisfactory nematocide effect have, in particular,
the compounds according .to the invention, in which I-Ilg
dipsaci
.
.
4-—N 0 1. 06115. CH2.S _________ __
noxyethyl group.
Excellent nematocides are compounds according to the
Table II states the results of a series of tests with 3
invention in which Hlg is a chlorine atom and R1 repre 50 n.butylmercapto-S-chloro-l.2.4-thiadiazole in vitro, car
sents a phenyl group, as well as those in which R2 repre
ried out as before. The table states the percentage of
sents an unbranched alkyl. group ‘comprising 51 to 6 car
nematodes killed within 140 hours’ exposition under the
bon atoms, an allyl group, an ethoxyethyl group or a
in?uence of the thiadiazole referred to.
phenyl-, 4-chlorophenyl or 4-methylphenyl group or a
TABLE II
55
benzyl- or 4-chlorobenzyl group.
Particularly those nematodes are attacked by com
Concentration of active substance
pounds according to the invention which cause eel worm
diseases in plants, for example Heterodera species, for
example larvae of Heterodera rostochz'ensis (potato cys
ticolous eel worm), Meloidogyne species (root knob eel 60
worms) Ditylenchus species (stem eel worms), Praty
lenchus species, Hoplolaimus species and larvae of An
guina triiicz‘ (wheat gall eel worms).
in parts per million
Nematode
500
100
50
25
12
100
Heterodera rostuchiensz's (larvae)___ 100
100
100
100
Ditylenchus dipsaci ..... -_
100
100
100
30
100
100
100
100
Anguinctritici (larvae)___
_
6
3
100
90
-.-__ ___
60 ___
Tests showing the nematocide etfect of compounds ac
cording to the invention were carried out as follows.
65
The e?ect of three compounds on nematodes in the
soil was investigated. The soil used was sandy, by its
nature strongly infected with Pratylenchus pratensis.
of polyethylenemonolaurate and subsequently suspended
In separate tests, samples of 250 gms. of the soil were
in 30 ccs. of water. By ‘diluting this suspension with
mixed with suspensions of 50, 25 and 10 mgms. respec
water suspensions of different concentrations were ob 70 tively of the substance to be tested in 12 ccs. of water
tained which were used for carrying out the tests.
and subsequently stored for 24 days in cups at approxi
1.5 ccs. of the suspension to be tested and subsequently
mately 15° C. In order to prevent drying out of the
30 mgs. of the compound to be tested were ?nely
ground with the addition of 5 drops of a solution of 5%
3,090,721
Goerdeler et al., Chem. Berichte 90, 182 et seq. and 892
et seq. (1957).) An amidin salt of isothiouroni-um salt
soil the cups were covered‘ with a polythene foil. The
nematodes were subsequentl-ywashed out of the soil in
the manner referred to by 'I. W. Seinhorst and the sur
in water in reacted with an equivalent quantity of per- ‘
chloromethylmercaptan with the addition of soda lye.
Several of the compounds according to the invention,
in which R1 represents the group R28 have, however, not
yet been mentioned in the literature. These compounds
vivors were counted (see Nematologica, vol. 1, pages 249
to 267 (1956)). The same was done with blank-tests
without adding active substance to the soil.
The tests were carried out ?ve times.
Table III states the average result of these tests for
each of the following compounds:
UE 9:3-phenyl-5-chloro-1.2.4-thiadiazole,
10 compounds are inter alia those in which in the aforesaid
I
formula R2 represents one of the following groups: iso
UE 18=B-methylmercapto-S-chloro-1.2.4-thiadiazole,
UE 19':3-n.butylmercapto~5-chloro-1.2.4-thiadiazole,
UE 32:3-n.propylrnercapto-5~chloro-1.2.4-thiadiazole.
TABLE n1
Compound
can be produced by the aforesaid method from iso~
thiouronium salts and perchloromethylmercaptan. Novel
propyl, l-methylpropyl, 3-methylpropyl, namyl, n.hexyl,
noctyl, n.dodecyl, allyl, ethoxyethyl, phenyl, '4-chl0ro
phenyl, 4-methylphenyl and phenoxyethyl.
15
Mg. active Surviving
Kill
substance per hematodes percentage
250 g. of soil
UE 9.-.; ..................... _.
UE 1s; ....................... -.
UE 19 ........................ -_
50
52
87
25
10
72
75
83
82
0
420
__________ -_
so
24
96
25
55
90
10
40
0
534
50
30
25
UE 32 ________________________ __
93
33
0
534
NE
I
25
lul
__________ _
94
.
94
.......... ..
25
32
96
10
5
52
50
93
93
0
758
.......... __
O-Cl
S
94
32
10
20
The production of a number of these novel compounds
will be described in Examples I to V.
Example I
vI‘I-PHENYLMERCAPTQ-5(THLORO-l.‘2AJFHIADIAZOLE
In a 3 litre ?ask, 188.5 gms. (1.0 mole) of phenyl
isothiouroniumchloride were mixed with 186 gms. (1.0
30 mole) of perchloromethylmercaptan, 180 ccs. of water
and 300 ccs. of methylenechloride, while cooling the ?ask
with ice-water. Subsequently, a solution of 160Jgms.
(4.0 mole) of sodium-hydroxide in 500 ccs. of water was
Principally known methods maybe used for producing 35 slowly added to the mixture, while'stirring vigorously.
The rate of adding the soda lye Was such that the tem
the pesticidal preparations. Thus, ‘for example, the ac
perature did not exceed 5° C. and the mixture did not
tive compounds according to the invention may be mixed
produce an alkaline reaction. After adding the whole
with a pulverulent inert carrier, for'exa-mple chalk, dolo
quantity, stirring was continued for half an hour. Sub
mite, attapulgite, kaolin or pipe clay, or dissolved or dis
persed in an inert solvent such‘ as toluene, xylene, aliphatic 40 sequently 25 ccs. of ammonia (25% by weight) were
added and further stirred for 15 minutes, followed by neu
‘or aromatic ketones, ‘for example acetone, methyl-ethyl
tralisation with hydrochloric acid.
a
ketone'or cyclohexanone, or mixtures of them with said
The layer of methylene chloride, in which the reac
hydrocarbons, if desired with the addition of surface-ac
tion product is ‘dissolved, was separated, washed with
tive materials and/or dispersion agentsj As an alterna
0.5 l. of water and dried on anhydrous sodium sulphate.
tive, these preparations may be mixed with synthetic ter
45 After distilling off the methylene chloride the residue,
tilisers.
that is the crude reaction product, was crystallised from
For example, a dust is prepared by grinding approxi
petroleum ether (boiling range 40° C. to 60° C.). Yield
mately 5 parts by weight of an active compound accord
148 gms. of 3-phenylmercapto-5-chloro~1.2.4-thiadiazole
ing to the invention together with approximately 95 parts
(yield 65%). Melting point 58° C.
by weight of kieselguhr to an average particle size of ap
50
The compounds used in the Examples II to V'were pro
proximately 10;r.
.
duced quite similarly.
For example a wettable powder is produced by mixing
‘approximately 50 parts by weight of an active compound
Example II
according to the invention with approximately 5 parts by
3-n.OCTYLMERCAPT’O-?-CHLORO-l.2A-THIADLAZOLE'
weight of oleylamido-methyltaurate, approximately 10
parts by weight of calciumligninsulfonate and approxi 55 22.4 gms. (yield 68%) of 3-n.octyl-mercapto-S-chloro
1.2.4-thiadiazole were obtained from 33.6 gms. (0.125
mately 35 parts by weight of dolomite (calcium-mag
mole) of n.-octylisothiouronium bromide and 23.3 ‘gms.
nesium carbonate), this mixture being ground to an aver
(0.125 mole) of perchloromethylmercaptan. Boiling
age particle size ‘of approximately 10;!“
point: 145° to 146° C. at 8 mms. mercury pressure.
Miscible oils may, for example, be produced by dis
solving approximately 25 parts by weight of an active 60
Example III
compound according to the invention in a mixture of
approximately 10 parts by weight of an active compound
according to the invention in a mixture of approximately
10 parts by weight of polyoxyethylenesorbitan fatty acid
ester, approximately 10 parts by weight of methylethyl
ketone and approximately 55 parts by weight of xylene.
The compounds according to the invention permit in
general,.miscible oils of :high concentration to be pro
duced. Thus, for example, 3-n.butylmercapto-S-chloro 70
1.2.4-thiadiazole with xylene can be worked up to a
3-ALLYLMERCAPTO-5-CHLORO-1.ZA-THIADIAZOLE
22.2 gms. (yield 46%) of 3-allylmercapto-5-chloro
1.2.4-thiadiazole were produced from 49.3 gms. (0.25
mole) of allylisothiouronium bromide and 46.5 gms. (0.25
mole) of perchloromethylmercaptan. Boiling point 115
117° C. at 15 mms. mercury pressure,
Example IV
v
3~(4=’-CHLOROBENZYL)MERCAPTO»5-CHLORO-1.2.4
THIADIAZOLE
miscible roil containing 80 percent by weight of active
17 gms. (yield 46%) of 3-(4’-chlorobenzyl)mercapto
material. This may be of importance in practice.
5-chloro-1.2.4-thiadiazole were produced ‘from 32 gms.
The production of a number of the compounds accord
(0.13 mole) of 4-chlorobenzylisothiouronium chloride
ing the invention has already been described. (See I. 75 and 25' gms. (0.13 mole) of perchloromethylmercaptan.
3,090,721
6
5
After crystallisation from .ligroin the melting point was
out in a solution of 12 gms. (0.120 mole) of cuprous
chloride in 120 ccs. of concentrated hydrochloric acid.
The 3-phenyl-5—chloro-1.2.4-thiadiazole was extracted
with petroleum ether (‘boiling range 40° C. to 60° C.)
from the reaction mixture. Yield 6.85 gms. (58%).
Melting point 42° C. to 50° C.
What is claimed is:
1. A composition for the control of nematode compris
52° C.
Example V
3- (4'-NITROBENZYL) MERCAPTO-5-CHLORO-1 2.4
THIADIAZOLE
14.5 gms. (yield 59%) of 3-(4'-nitrobenzyl)mercapto
5-chloro-1.2.4-thiadiazole were obtained from 25 gms.
(0.086 mole) of 4-nitrobenzylisothiouronium bromide
and 16 gms. (0.086 mole) of perchloromethylmercap
tan.
ing as an active ingredient a thiadiazole compound cor
After crystallization from a mixture of benzene 10 responding to the general formula:
and ligroin '(l : l) the belting point was 97° C.
In Table IV are listed the yields obtained by the .pro
duction method described in the aforesaid examples and
physical constants of several novel 5-chloro-1.2.4-thia
15 wherein Hal represents a halogen atom and R1 represents
diazoles according to the invention.
a radical selected from the group consisting of phenyl
TABLE IV
and the radical R28 wherein R2 represents a radical se
'lected from the group consisting of alkyl, alkoxy- alkyl,
R2-—S——C—~—N
II
II
N
C——Cl
allyl, phenyl, methylphenyl, chlorophenyl, benzyl, chlo
Melting Boiling point ° 0. at mm. Yield,
point,
percent 20
mercury pressure
robenzyl and phenoxyethyl in a nematocidal effective
amount, a surface active material and a nematocide ad
juvant as a carrier therefor.
° 0.
2. The composition of claim 1 wherein Hal represents
a chlorine atom.
110° to 112° at 14 mm ____ __
126° to 128° at 14 mm___
122° to 124° at 14 mm...
102°
110°
145°
180°
to
to
to
to
25
_
46
_
en
3. The composition of claim 1 wherein R2 represents
an alkyl radical containing 1 to 12 carbon atoms.
104° at 0.7 mm._._.
112° at 0.02 mru____
146° at 0.8 mm_____
183° at 0.05 mm____
12
65
échlorophenyl ______ __
25
4-methylphenyl
Phenoxyethyi
51
40
4-chlor0benzyl ______ -_
a-uitroheuzyl _______ -_
46
59
It was moreover found that the compounds according
to the invention can be produced from the correspond
ing 5-amino-l.2.4-thiadiazoles according to the reaction
of Sandmeyer, in which the amino compounds are con
4. The composition of claim 1 wherein R2 represents
the ethoxyethyl radical.
5. The composition of claim 1 wherein R2 represents
30 an nnbranched alkyl radical containing from 1 to 6 car
bon atoms.
6. A dust for combating nematodes comprising an in
timate mixture of about 5 parts by weight of the active
compound of claim 1 and about 95 parts by weight of
35 kieselguhr, said dust having an average particle size of
approximately 10;!“
7. A wettable powder for combating nematodes com
prising an intimate mixture of about 50 parts by weight
of the active compound of claim 1, about 5 parts by
verted into diazonium compounds by means of nitrite, for 40 weight of oleylamidomethyllaurate, about 10 parts by
example sodium nitrite, which diazoniurn compounds are
Weight of calcium ligninsulfonate and about 35 parts by
converted into S-chloro-1.2.4-thiadiazoles in the presence
weight of dolomite, said powder having an average parti
of copper powder and a chloride, or in the presence of,
cle size of about 10a.
for example, cuprous chloride.
8. A miscible oil for combating nematodes compris
This method will be set out in the following examples.
45 ing a solution of about 25 parts by weight of the active
compound of claim 1 in a mixture of about 55 parts by
Example VI
‘3-BENZYLMERCAPTO-5—CHLORO-1.2.4-THIADIAZOLE
9.5 gms. (0.043 mole) of 3-benzyhnercapto-5-amino
1.2.4-thiadiazole were dissolved in 100 ccs. of acetic acid.
Whilst cooling with ice a solution of 4.9 gms. (0.07 mole)
of sodium nitrite in 50 ccs. of concentrated hydrochloric
acid was added dropwise such that the temperature of the
mixture did not exceed 20° C. After standing 15 min
weight of xylene, of about 10 parts by weight of methyl
ethyl-ketone and of about 10 parts by weight of polyoxy
ethylene-sorbitan fatty acid ester.
9. A composition for the control of nematodes com
prising as an active ingredient 3-phenyl-5-chloro-l,2,4
thiadiazole in a nematocidal effective amount, a surface
active material and a nematocide adjuvant therefor.
10. A composition for the control of nematodes com
prising as an active ingredient 3-alkylmercapto-5-chloro
poured out while stirring, in a solution of 6 gms. of 55
1,2,4-thiadiazole in a nematocidal effective amount, a
cuprous chloride in 100 ccs. of concentrated hydrochloric
surface active material and a nematocide adjuvant there
acid. After standing overnight, the mixture obtained
for.
was shaken with benzene at room temperature. After
11. A composition for the control of nematodes com
concentration by evaporation, the benzenic solution
prising as an active ingredient 3-ethoxyethylrnercapto-5
yielded 5.9 gms. (60%) of crude 3-benzylrnercapto-5 60
chloro-l,2,4-thiadiazole in a nematocidal effective amount,
chloro-1.2.4-thiadiazole from which the pure compound
a surface active material and a nematocide adjuvant
was obtained by crystallization from methanol. Melt
therefor.
ing point 49° C.
12. A composition for the control of nematodes com
EXAMPLE VII
65 prising as an active ingredient 3-phenylmercapto-5-chloro
3-PHENYL—5—CHLORO-1.2.4—THIADIAZOLE
1,2,4-thiadiazole in a nematocidal effective amount, a
surface active material and a nematocide adjuvant there
This compound was produced in a manner similar to
for.
that used in Example V1.
13. A composition for the control of nematodes com
10.6 gms. (0.06 mole) of 3-phenyl-5-amino-1.2.4-thia
diazole were dissolved in 130 ccs. of acetic acid, followed 70 prising as an active ingredient 3~n-butylmercapto-5-chlo
by adding, while stirring, a solution of 4.56 grns. (0.066
ro-l,2,4-thiadiazole in a nematocidal effective amount,
a surface active material and a nematocide adjuvant there
mole) of sodium nitrite in 45 ccs. of concentrated sul
for.
phuric acid. The temperature was kept between 5° C.
14. A composition for the control of nematodes com
and 10° C. Subsequently, the temperature of the mix
ture was raised to 18° C. and the mixture was poured 75 prising as an active ingredient 3-methylmercapto-5-chlo
tries at room temperature, the reaction mixture was
3,090,721
8
r0-.1,2,4-thiadiazole in a nematocidal e?ective amount, a
surface active material and a nematocide adjuvant there
23.- A method of combating nematodes comprising
treating the habitat thereof with the composition of
for.
15. A composition for the control of nematodes com
prising as an active ingredient 3-(41-ch1orophenyl)-mer
capto-S-chloro-1,2,4-thiadiazole in a nematocidal effec
claim 12.
24. A method of combating nematodes comprising
treating the habitat thereof with the composition of
tive amount, a surface active material and a nematocide
25. A method of combating nematodes comprising
treating the habitat thereof With; the composition of
claim 13.
adjuvant therefor.
'
claim 14.
V
V
16. A composition for the control of nematodes com
26. A method of combating nematodes comprising
prising as, an active ingredient 3-(41-methylpheny-D-mer 10
treating the habitat thereof with the composition of
capto-S-chloro-l,2,4-thiadiazole in a nematocidal effective
claim 15.
27. A method of combating nematodes comprising
amount, a surface active material and a nematocide ad
juvant therefor.
treating the habitat
17. A composition for the control of nematodes com
prising as an active ingredient S-benzylmercapto-5-chloro 15 claim 16.
28. A method of
1,2,4-thiadiazole in a nematocidal effective amount, a
treating the habitat
surface active material and a nematocide adjuvant there
claim 17.
for.
29. A method of
18. Acomposi-tion for the control of nematodes com
prising-as an active ingredient 3-(41-henzylmercapto)-5 20 treating the habitat
claim 18.
chloro-1,2,4—thiadiazole in a nematocidal effective amount,
thereof with the composition of
combating nematodes comprising
thereof with the composition of
combating nematodes comprising
thereof with the composition of
a surface active material and a nematocide adjuvant
therefor.
19. A method of
treating the habitat
claim 1.
20.- A method of
treating the habitat
claim
9.
21.»A- method of
treating the habitat
claim 10.
22. A method of
treating the habitat
claim 11.
References Cited in the ?le of this patent
combating nematodes comprising
thereof with the composition of 25
combating nematodes comprising
thereof with the composition of
V
a /
combating nematodes comprising 30
thereof with the composition of
UNITED STATES PATENTS
2,285,410
2,592,195
Bousquet et a1. ________ __ June 9, 1942
Schwarz _______ _'___V.___. Apr. 8, 1952
2,702,803
2,744,908
2,863,804
Ainsworth ___________ 2. Feb. 22, 1955.
Young ______________ __ May 8, 1956
Benghiate et a1. _______ __ Dec. 9, 1958
'
combating nematodes comprising
thereof with the composition of
OTHER REFERENCES
Agr. and Food Chem., vol. 5, pages 159-160, March
CAD U! 1957.
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