Note: Descriptions are shown in the official language in which they were submitted.
~8~3~
OOZo ~2~106
ISOXAZOLYLMETHYLTHIOL CARBAMATES
The present invention relates to new and valuable
isoxazolylmethylthiol carbamates, herbicides containing these
compounds, and methods of controlling the growth of unwanted
plants with these compounds.
It is known from French 2~205,514 that the thiolcarbamic
acid esters of imidazole have a herbicidal action.
There is no disclosure of the type of herbicidal
activity, e.g., selectivity in and tolerance by crop plants,
and application rates. The herbicidal action of the active
ingredients is only slight.
Numerous thiol carbamates are known as herbicides. Some
of them have achieved considerable importance in agriculture
and horticulture for controlling the growth of unwanted plants.
A characteristic common to these compounds is the good action
on unwanted grasses. However, this action varies from species
to species of this family. For instance, N,N-dipropylthiol-
ethyl carbamate controls wild oats (German Published Appli-
cation DAS 1,031,571), but this species is not listed in the
manufacturer's recommendations for N,N-dipropylthiolpropyl
carbamate (German Published Application DAS 1,031,571). It is
reported that N,N-dipropylthiolethyl carbamate has a good
; action on Setaria spp., whereas the action Or N,N-diisopropyl-
thiol-2,3-dichloroallyl carbamate (German Published Appli-
.~
~a
8133
0 Z. 32,106
cation DAS 1,142,464) was inferior here. In addition to con-
trolling unwanted grasses, some compounds of this class also
destroy Cyperaceae and some broadleaved weedsO For instance,
N,N-dipropylthiolpropyl carbamate has an extremely reliable
action on Cyperus spp., whereas N,N-diisopropylthiol-2,3-
dichl~oallyl carbamate has practically no effect on these
species An essential criterion for the use of these agents
is the difference in selectivity from crop plant to crop
plant. Thus, N-ethyl-N-cyclohexylthiolethyl carbamate
(British 995,316) i!s used predominantly in Beta beets. Tne
most important crop plant for N,N-diisobutylthiolethyl
carbamate (German Published Application DAS 1,031,571) is
Indian corn. This difference is particularly surprising in
the case of N,N-diisopropylthiol-2,3-dichloroallyl carbamate
and N,N-diisopropylthiol-2,3,3-trichloroallyl carbamate
(German Published Application DAS 1,142,464). Both products
can be employed without diff;culty in broadleaved crops such
as beet and rape. For cereals, the manu~acturers and
distributors only recommend N,N-diisopropylthiol-2,3,3-tri-
chloroallyl carbamate, as it i8 less aggressive in these
crops.
Prior art thiol carbamates have in general a high vapor
pressure, as the following list shows:
Active ingredient vapor pressure mm Hg at C
N,N-dipropylthiolethyl
carbamate 34 x 10 3 25
N,N-diisobutylthiolethyl
carbamate - 2 - x 10 3 25
, ' ~
11`~8133
O.Z. 32,106
N,N-dipropylthiolproDyl
carbamate 10.4 x 10 3 25
N-ethyl-N-cyclohexylthiol-
ethyl carbamate 6.2 x 10 3 2
N,N-diisopropylthiol~2,3-
dichloroallyl carbamate 1.5 x 10 4 25
N,N-diisopropylthiol-2,3,3-
trichloroallyl carbamate 1.2 x 10 4 25
hexahydro-lH-azepine-1-
carbamic acid thiolethyl
ester 5.6 x 10 3 25
(German 1,300,947)
All these compounds have to be incorporated into the soil
to prevent loss through evaporationO In the case of the last
compound, the submerging of rice paddies probably has the same
effect as incorporation.
Although generally speaking the incorporation of herbi-
cides is positive for a number of reasons, this method of
application does have considerable disadvantages, e.g., the
- work burden is increased, and special incorporation equipment
has to be acquired. This makes itself felt particularly at
farms having a low degree of mechanization. The seedbed is
excessively lo~sened, and as a consequence certain seeds have
emergence difficulties in dry weatherO In areas where heavy
rainfalls occur, this additional soil treatment increases
the risk of erosion, particularly on sloping ground.
Similarly, loosening of the soil assists wind erosion in arid
wind-swept tracts. For these reasons, attempts are made under
the abovementioned conditions to move the soil as little as
,
-- 3 --
33
possible during cultivation ("reduced tillage").
There is therefore a demand for active ingre-
dients which offer an alternative to incorporation. In the
field of thiol carmamates with their specific properties, such
compounds, with the exception of hexahydro-lH-azepine-l-carba-
mic acid thiolethyl ester and S-(4-chlorobenzyl)-N,N-diethyl-
thiol carbamate - which are used in rice -, have hitherto not
been available. Attempts have recently been made in this di-
rection with the manufacture of thiol carbamate sulfoxides. :
lGWe have now found that isoxazolylmethylthiol
carbamates of the formula
N ~ -S-C-N /
R4 ~ \ R6
.~
where R1 denotes hydrogen, alkyl, unsubstituted or alkyl-sub~ .
stituted cycloalkyl, aralkyl, unsubstituted or halogen-sub-
stituted phenyl, R2 denotes hydrogen, alkyl, aryl, or halogen,
R3 denotes hydrogen or alkyl, R4 denotes hydrogen or alk.yl, and
R5 and R6 are identical or different and each denotes alkyl,
alkenyl, unsubstituted or alkyl-substituted cycloalkyl, al-
koxyalkyl or haloalkyl, and additionally R5 and R6 together
with the nitrogen atom denote an unsubstituted or a lower alkyl-
substituted azetidine, pyrrolidine, piperidine, hexahydroazepine,
heptamethyleneimine, bicyclo-(3,2,2)-3-azanonane or morpholine
: radical,have a strong herbicidal and selective action.
These active ingredients offer, in addition to
the wider spectrum of action, a flexibility in the method of
application hitherto unknown in this class of compounds.
"'~
O O Z D 32,106
The radicals R contained in the isoxazolylmethylthiol
carbamates of the formula I have for instance the following
meanings:
R = hydrogen; lower alkyl of a maximum of 6 carbon atoms,
eOgO, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-
butyl, isobutyl, tert-butylg n-pentyl, 2-pentyl,
3-pentyl, n-hexyl; cycloalkyl of a maximum of 8 carbon
atoms optionally substituted by lower alkyl, e.g., cyclo-
propyl, cyclopentyl, cyclohexyl, cyclooctyl; aralkyl,
e.g., benzyl9 1-phenylethyl, 2-phenylethyl; and
optionally substituted aryl, e~gO, phenyl, chlorophenyl,
fluorophenyl, dichlorophenyl, trifluoromethylphenyl;
; R2 = hydrogen; optionally substituted lower alkyl of a maximum
of 6 carbon atoms, e.g., methyl, ethyl, isopropyl,
chloromethyl; aryl, eOgO, phenyl; and halogen, e.g.,
chloro, bromo, iodo;
R3 and R4 = hydrogen, and lower alkyl, especially methyl;
; R5 and R6 = lower alkyl of a maximum of 6 carbon atoms, e.g.,
methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-
butyl, isobutyl, n-pentyl, 2-pentyl, 3-pentyl,
n-hexyl; lower alkenyl of a maximum of 4 carbon
atoms, eOg., allyl, methallyl, but-2-en-1-yl, but-
4-en-1-yl; cycloalkyl of a maximum of 8 carbon
atoms optionally substituted by lower alkyl, e.g.,
cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl,
2-methylcyclopentyl; alkoxyalkyl of a maximum of
6 carbon atoms, eOgO, 2-methoxyethyl, 2-ethoxy-
ethyl, 1-methoxy-2-propyl, 3-methoxypropyl; halo-
-- 5 --
Bi33
O~ZO 32,106
alkyl of a maxlmum of 4 carbon atoms, eOg.,
2-chloroethyl, 1-chloro~2-propyl~ 3-chloropropyl,
R5 and R6 together with the nitrogen atom may also
denote a heterocyclic ring of a maximum of 10 car-
bon atoms optionally substituted by one or more
; lower alkyl groups, eOg~, azetidine, 2-methyl-
azetidine, 2,4-dimethylazetidine, 2,4,4-trimethyl-
azetidine, pyrrolidine, 2-methylpyrrolidine, 2-
ethylpyrrolidine, 2,5-dimethylpyrrolidine,
piperidine, 2-methylpiperidine, 2-ethylpiperidine,
2-methyl 5-ethylpiperidine, hexahydroazepine,
2-methylhexahydroazepine, 2,3-dimethylhexahydro-
azepine, heptamethylenimine, bicyclo- C3,2,2~ -3-
azanonane, morpholine, 2,6-dimethylmorpholine,
3,5-dimethylmorpholineO
The compounds according to the invention of the formula I
may be prepared in accordance with the equation below by :
; reaction of an isoxazolyl methyl halide or isoxazolyl methyl-
alkane sulfonate with a salt of a thiol carbamate.
: 20 Process A:
R1 /R2
~ N~ ~ - X + M-S-C N ~' R
-~ R4 \ R6
II III
Rl ,R2
N~ ~ R3 0 / R5
0 C -S-C-N \ + M-X
R4 I R6
11~8133
OOZo 32,106
R1 to R6 ha~e the abovementioned meanings; X denotes halogen
or alkane sulfonate and M an alkali metal atom or ammonium
optionally substituted by 2 or 3 alkylsO The starting
materials of the formula II employed in process A are known or
may be prepared by reaction of nitrile oxides with acetylene
: halidesO Examples of such compounds are 5-chloromethyl-3-
methylisoxazole, 5-bromomethyl-3-ethylisoxazole, 5-chloro-
methyl-3-isopropylisoxazole, 5-bromomethyl-3-tert-butyl-
isoxazole, 5-chloromethyl-3,4-dimethylisoxazole, 5-(1'-chloro-
ethyl)-3-methylisoxazole, 5-bromomethyl-3-phenylisoxazole,
5-chloromethyl-3-(3',4'-dichlorophenyl)-isoxazole, and 5-
bromomethyl-3-cyclohexylisoxazoleO The compounds 5-chloro-
methylisoxazole and 5-bromomethyl-3-methyl-4-chloro (or
4-bromo)-isoxazole are known from the literature (Kochetkow
. and coworkers, Chemical Abstracts, 47, 2167, 1953; Khim.
GeterotsiklO SoedinO, 1974, 602)o The corresponding isoxazolyl
methylalkane sulfonates may be prepared from prior art
isoxazolyl methanols (Gazz~ chimO italO, 69, 536, 1939) in con-
ventional manner by reaction with alkanesulfonic acid
chlorides in the presence of agents which bind hydrogen
chloride, eOgO, pyridineO The isoxazolyl methyl halides may
~or instance be prepared as follows:
Specification A1
. FH2-Br
., CH3 N~0
'.1
238 g (parts by weight) of propargyl bromide, 476 g
-- 7 --
;
~8133
0.Z. 32,106
(parts by weight) of phenyl isocyanate and 158 g (parts by
weight) of nitroethane are dissolved in 1500 ml of toluene;
at 15 to 20C, 1 ml of triethylamine (to activate the phenyl
isocyanate) is added. The temperature is kept at from 15 to
30C for 3 hours, and 1 ml of triethylamine (4 ml in all) is
added each hour. The mixture is then stirred for 1 hour at
70C and then cooled~ The precipitate is suction filtered and
the residue rinsed with 1 l of toluene. The combined filtrates
are concentrated and the residue is distilled under an oil
pump vacuum. At 59 to 61C/002 mm Hg, 310 g (~ 88% of theory)
of 3-bromomethyl-5-methylisoxazole distils over (n25: 1.5168).
C5H6BrN0 (176)
C H N Br
CalcO: 34~2 3O4 7.9 45.5
Found: 34Oo 3.4 8.o 45O4
60 MHz nmr spectrum (CDC13; ~ values) 2.3 (3H, s), 4.44 (2H,s),
6015 (lH, s)
13C nmr spectrum (CDCl3, ppm values relative to TMS):
167.2 (C), 16001 (C), 10405 (CH), 18.8 (CH2), 11.3 tCH3).
Specirication A2
3 ~ CH3
N~
93.5 g (parts by weight) of acetohydroximoyl chloride
(Ber. dtsch. chemO Ges., 40, 1677~ 1907) and 90 g (parts by
weight) of isobutynyl chloride are stirred in 1500 ml of
; - 8 -
~8~
OoZo 32~106
benzene; at 15 to 20 C, 105 g ~parts by weight) of triethyl-
amine is added dropwise~ The mixture is then stirred for
1 hour at from 20 to 25C and for 1 hour at 70Co After the
mixture has been allowed to cool it is filtered and the fil-
trate concentratedO The distillate wh;ch remains is distilled
under an oil pump vacuumO There is obtained 133 g (92% of
theory), bopo 48 to 50C/0005 mm Hg; n25- 1047400
C6HgNOCl (14505)
C H N Cl
Calc.: 4906 505 907 2405
Found: 49~5 507 lOoO 2400
60 MHz nmr spectrum (CDCl3, ~ values) 1078 (d, 3H), 2.3
(s, 3H), 5~05 (9~ lH), 6009 (s~ lH)o
3C nmr spectrum (CDCl3, ppm values relative to TMS):
171~5 (C)~ 15908 (C)~ 10205 (CH)~ 4704 (CH), 23.3 (CH3),
11~ 5 (CH3)o
Sepcification A3
C2H5
N~O~CH2-Br
119 g (parts by weight) of propargyl bromide, 95 g (parts
by weight) of nitropropane and 440 g (parts by weigh) of tri-
ethylamine are dissolved in 1200 ml of chloroform; at 0C,
155 g (parts by weight) of phosphoroxy chloride is added drop-
wiseO The mixture is kept at 20C for 30 minutes and refluxed
for 2 hours. After the mixture has been cooled, filtration
; and concentration are carried out 3 and the residue is taken
_ g _
-
li'~8~33
0,Z. 32,106
up in water. The water phase is extracted several times with
toluene and the combined toluene phases are washed with water
and subsequently dried over sodium sulfate. The sodium sulfate
is then separated and the filtrate concentrated; the residue
is distilled under an oil pump vacuumc At 78 to 79C/0.1 mm
Hg, 150 g (79% of theory) distil off; nD5 : 1.5108.
C6H8BrNO ( 190 )
C H N Br
Calc.: 3709 407 704 4200
Found: 3800 406 7.6 41.7
The following compounds are obtained analogously:
3 ~ n25 = 104806
CH2-C
CH3 ~ CH2-~ nDS : 1.5500
C 2H5 ~
CH 51
i-C3H7-S-cH2~c~H3
CH-Br
i-C3H7~clH3
CH-Cl
-- 10 --
. .
~8133
OOZo ~2,106
CH3-0-CH2 ~3~
C~12 Cl
The compounds designated w;th formula III are salts of
thiolcarbamic acidsc Typical representatives, which may be pre-
pared in conventional manner, are the sodium salts or the
ammonium salts - optionally substituted by 2 or 3 alkyls - of
N,N-dimethylthiolcarbamic acid~ N,N-diethylthiolcarbamic acid,
N,N-diisopropylthiolcarbamic acid, N,N-di-n-propylthiolcar-
bamic acid, N,N-di-n-butylthiolcarbamic acid, N,N-diisobutyl-
thiolcarbamic acid, N-ethyl-N~n-butylthiolcarbamic acid,
N-ethyl-N-isopropylthiolcarbamic acid, N-ethyl-N-cyclohexyl-
thiolcarbamic acid, ~,N-diallylthiolcarbamic acid, further
N-azetidine-, N-pyrrolidine-, N-piperidine- and N-hexahydro-
azepinethiolcarbamic acid and their derivatives substituted in
the ring by 1 to 3 methyl and/or ethyl groups.
Process A may be carried out in the presence of any inert
organic solvents, for instance hydrocarbons, e.g., cyclo-
hexane, benzene, toluene; halogenated hydrocarbons, e.g.,
methylene chloride, chloroform, carbon tetrachloride, chloro-
benzene; ethers, e.g., diethyl ether, diisopropyl ether,
tetrahydrofuran, dioxane, glycol dimethyl ether; lower alco-
hols and ketones, e.gO, methanol, ethanol, isopropanol,
acetone, methyl ethyl ketone, cyclohexanone; nitriles9 eOg.,
acetonitrile; and water. Mixture of these solvents may also be
usedO
For the preparation of the new active ingredients, pro-
cess A is preferredO
-- 11 --
8~3
O.Z. 32,106
If desired, the isoxazolylmethylthiol carbamates of theformula I according to the invention may also be prepared in
accordance with process B by reaction of isoxazolylmethyl mer-
captans or their salts with carbamic acid chlorides
Process B
R1 2 1 2
R3 ~, / R5 N ~ R ~ R5
C-S-Y + Cl-C-N - ~ C-S-CO-N ~ + Y-Cl
R4 \ R6 R4 R6
IV V
In the formulae, R1 to R6 have the above meanings and Y
denotes hydrogen, an alkali metal atom, or ammonium optionally
substituted by 2 or 3 alkyls. -~
Formula IV represents starting materials which may be
prepared by conventional methods from the isoxazolyl methyl
halides of the formula II by reaction with hydrogen sulfide
or salts thereof (e.g., Houben-Weyl, Methoden der Organischen
Chemie, IX, 1-18)o The following are examples of mercaptan5 of
the formula IV: 3-methylisoxazoly1-5-methyl~ercaptan, 3-
ethylisoxazolyl-5-methylmercaptan, 3-phenylisoxazolyl-5-
methylmercaptan, 3-methylisoxazolyl-5-(1'-ethyl)-mercaptan.
Examples of carbamoyl chlorides of the formula V are
those of dimethylamine, diethylethylamine, di-n-propylamine,
diisopropylamine, di-n-butylamine, N-ethyl-n-butylamine,
N-ethyl-n-isopropylamine, azetidine, pyrrolidine, piperidine,
hexahydroazepine and derivatives thereof substituted on the
ring by 1 to 3 methyl and/or ethyl groups.
- 12 -
''
. .
~.Z0 32,106
Process B is expediently carried out in the presence of
a hydrogen chloride acceptorg Suitable for this purpose are
any inorganic bases, eOg., alkali metal bicarbonates,car-
bonates and hydroxides; organic bases, such as alkali metal
alcoholates, e.g~, sodium methylate; tertiary amines, e.g.,
triethylamine and N,N-dimethylcyclohexylamine; and saturated
or unsaturated nitrogen heterocycles, eOg., N-methylpiperidine,
pyridine and quinoline. The process is advantageously carried
out using one of the solvents (or mixtures thereof) listed at
process Ao
The isoxazolylmethylthiol carbamates of the invention of
the formula I may also be prepared by reaction of an isoxa-
zolylmethylthiochlorocarbonic acid ester with a secondary
amine.
Process Co
,
R ~ R1 2
N ~ R3 0 / R5 N ~ ~ " / + HCl
C-S-C-Cl + HN ~ C-S-0-N
R4 ~ R6 R4 ~ R6
VI VII
In the formulae, R1 to R6 have the abovementioned
meanings.
The thiochlorocarbonic acid esters of the formula VI may
be prepared in conventional manner from the isoxazolylmethyl-
mercaptans Or the formula IV (Y = hydrogen) and phosgene.
Examples of compounds of the formula VI are 3-methylisoxa-
zolyl-5-methylthiocarbvn~l chloride, 3-ethylisoxazolyl-5-
.
- 13 -
8133
OOZo 32,106
methylthiocarbonyl chloride3 and 3-phenylisoxazolyl-5-methyl-
thiocarbonyl chloride. Suitable secondary amines of the for-
mula VII are particularly those listed at process B as compo-
nents of the carbamic acid chloridesO Process C may be carried
out using the inert solvents mentioned in process A - less
advantageously in alcohols or water - and with or without the
addition of one of the hydrogen chloride acceptors mentioned
in process Bo
In detail, process A may for instance be carried out as
follows.
At from -20 to ~50C, 1 mole of an isoxazolylmethyl
halide or alkane sulfonate of the formula II, optionally in
one of the above solvents, is dripped into a solution or sus-
pension of at least 1 mole of a thiol carbamate of the for-
mula III~ To complete the reaction, the mixture is stirred for
from 3 to 12 hours at from 0 to to 80Co Upon completion of
the reaction, the mixture is poured into water and the pro-
duct is extracted, if desired with an inorganic solvent
immiscible with water, and subsequently isolated by distil-
lation or crystallization,
Process B may for instance be carried out in the follo-
wing manner.
A solution of 1 mole of isoxazolylmethylmercaptan of the
formula IV in a solvent is reacted with at least one mole of a
carbamic acid chloride of the formula V in the presence of at
leat 1 mole of one of the abvementioned inorganic or organic
bases at from -10 to +80C and for from 1 to 12 hours The
thiol carbamates according to the invention of the formula I
33
O.Z. 32,106
are isolated as described aboveO
Process C is for instance carried out as follows~
A solution Or 1 mole of a thiochlorocarbonic acid ester
of the formula VI in an inert organic sol~ent is reacted with
at least 1 mole of an amine of the formula VII; the acid-
binding agent may be at least 1 mole of the inorganic or
organic bases mentioned in process Bo The reaction temperature
is from -10 to +80 C and the reaction time from 1 to 12 hours,
as in process B, depending on the reactants, the base and the
solvent employed. The thiol carbamates are isolated as
described above~
The following examples, in which the parts are by weight,
illustrate the processes for preparing the isoxazolylmethyl-
thiol carbamates according to the in~ention of the formula I.
EXAMPLE
At 0C, 60.0 parts of carbonyl sulfide was gassed into a
mixture of 102 parts of N-ethylcyclohexylamine, 80.8 parts of
triethylamine and 700 parts of methylene chloride, and the
whole was stirred for 2 hours at room temperature. Subsequent-
ly, 105.3 parts of 3-methyl-5-chloromethylisoxazole was
dripped in over a period of 1 hour at 0C, and the mixture
stirred for 10 hours at room temperature. The salt which had
formed was filtered off and the filtrate was washed
successively with water, lN hydrochloric acid and again with
water, and dried. After removal Or the solvent, distillation
of the residue gave 194.2 parts of 3-methyl-5-isoxazolyl-
methyl-N-ethyl-N-cyclohexylthiol carbamate, b.p. (0.2 mm Hg)
176-179C (m.p. 60-62C)
- 15 -
O.Z0 32~106
EXAMPLE 2
At 0C~ 8.0 parts of carbonyl sulfide was gassed into a
mixture of 2102 parts of diisopropylamine in 100 parts of
toluene, and the whole stirred for 30 minutes at 0C and for
1 hour at room temperature. Subsequently, 19.0 parts of 3-
ethyl-5-bromomethylisoxazole was dripped in over a period of
15 minutes and the whole stirred for 3 hours at room tempera-
ture. After working up as in Example 1, there was obtained
21.8 parts of 3-ethyl-5-isoxazolylmethyl-N,N-diisopropylthiol
carbamate having a boiling point at 0.3 mm Hg of 154-156C
(nD5: 105089).
EXAMPLE 3
While cooling, 2908 parts of N,N-diethylcarbamic acid
chloride was dripped into a mixture of 2508 parts of 3-methyl-
isoxazolyl-5-methylmercaptan in 100 parts of ether and
50 parts of pyridine; the whole was then refluxed for 3 hours.
After working up as in Example 1, there was obtained 35.8
parts of 3-methyl-5-isoxazolylmethyl-N,N-diethylthiol
carbamate having a boiling point at 0.05 mm Hg of 136-138C.
; The following isoxazolylmethylthiol carbamates according
to the invention may be prepared by one of the abovementioned
processes.
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- 16 -
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~1~8:133
O. Z . 32, 106
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0 Zq 32,106
Examples demonstrating the herbicidal action of the new
isoxazolylmethylthiol carbamates
A series of experiments, divided in the main into the
follo~ing three groups, was carried out to provide evidence in
support of the statements made in the introduction about these
active ingredientsO
I Greenhouse experiments
.
The vessels employed were paraffined paper cups having a
volume of 200 cm3, and the substrate was a sandy loam con-
taining about lo 5% (wt%) humusO The seeds of the test plantswere sown shallow and separated according to speciesO The
active ingredients were applied immediately (preemergence
treatment), suspended or emulsified in water as the
distribution medium and sprayed onto the soil surface by means
of finely distributing nozzles. Prior to the chemical treat-
ment, the cups were lightly sprinkler-irrigated; the agents
therefore came into contact with moist soilO After application
of the agents the vessels were covered with transparent
plastic hoods until the plants had taken root. This cover pre-
vented the evaporation of water and readily volatile sub-
stances. Another effect was the more uniform emergence of the
test plants, to the extent that they were not impaired by
chemicals. When postemergence treatment was employed, the
plants were first grown in the vessels to a height of from 3
to 10 cm~ depending on the form of growth, and then treated~
A cover was not used~ Depending on the temperature require-
ments of the plants, the experiments were set up either in the
cooler (10-20C) or warmer (18-30C) portion of the green-
- 22 -
: .
. , .
~iU~1~33
O.Z0 32,106
house. The experiments lasted for from 2 1/2 to 6 weeks.
During this period, the plants were tended and their reaction
to the individual treatment was evaluated. The substances
examined, the dose rates employed (in kg/ha of active
ingredient) and the types of plant used in the experiments are
given in the following tables. A 0 - 100 scale was used for
assessment, 0 denoting no damage or normal emergence, and 100
denoting complete destruction or non-emergence.
IIo Experiments in the open
These experiments were carried out on small plots of
various sizesO The soil was a sandy loam having a pH of 5-6
and 1 - lo 5% humusO The compounds were applied from early to
late fall and from early to late spring, corresponding to the
sowing period for the crop plantsO The compounds were emulsi-
fied or suspended in water as carrier and distribution medium,
and applied by means of a motor-driven plot spray mounted on
a hitcho The application methods most frequently employed were
preplant incorporation and preemergence surface application.
In individual experiments, the action of the agents when
sprayed during emergence of the crop plants and weeds, and
postemergence after formation of a few genuine leaves was
examined. All the experiments were run for several months;
during this period assessments were made at certain intervals
employing the 0 to 100 scaleO
IIIo Herbic_dal action via the vapor phase
The remarkable herbicidal action of isoxazolylmethyl-
thiol carbamates, even when not incorporated into the soil as
is necessary with prior art thiol carbamates, suggested that
- 23 -
3~
0uZO 32,106
the losses of active ingredient through evaporation were low.
To examine this, the following experiment was carried out in
the greenhouse~ Seeds of a sensitive oat crop were sown as
described in Section I (greenhouse experiments) and treated
with the herbicidal active ingredients at various rates. The
vessels were not however covered with a plastic hood, but
placed in pairs in 5 liter glass cylindersO The pairs were
made up Or a treated and an untreated vesselO ~or comparison
purposes, control cylinders containing only untreated pots
were usedO To prevent gas exchange with the atmosphere, the
rims of the cylinders were coated with Vaseline and the
opening was covered with a glass plateO Readily evaporating
substances were thus able to escape from the surface of the
soil in the vessels into the cylinder space and possibly
influence the germination and development of the test plants
in the parallel vessels originally free from active
ingredient. The temperature in the glass cylinders varied
from 11C in the morning to 30C in the afternoon in sunlight.
After 14 days, the plants in the control cylinders had
reached a height of from 13 to 15 cm and the differences be-
tween the various treatments were readily perceptible. In
addition to a visual assessment~ the green weight of the oat
shoots was determined for each vesselO This is given in
Table llo
Results
The individual results from the various experiments and
tables combine to give the following pictureO
1) The introduction of the isoxazolylmethyl radical into the
- 24 -
8~33
00%0 32,106
thiol carbamates resulted in a shirt in action, parti-
cularly in a broadening of the range Of action compared
with prior art thiol carbamatesc Thus, for instance~ some
compounds developed an actlvity embracing that Of N,~-di-
isopropylthiol-2,3-dichloroallyl carbamate or N,N diiso-
propylthiol-2,333-trichloroallyl carbamate and of N,N-
dipropylthiolethyl carbamate (cfo Tables 2, 3 and 5)0 In
other instances, a similar, at times somewhat poorer, her-
bicidal performance to that N-ethyl-N-cyclohexylthiolethyl
carbamate was found~ However~ the selectivity range in crop
plants was incomparably greater (cfo Table 6) It should be
pointed out at this juncture that the prior art thiol
carbamates were only employed in the experiments because Of
their action as herbicidesO Compounds having a structure
similar to that of the compounds of the invention are
hitherto unknown. A thiol carbamate having a heterocyclic
; ring and known as a herbicide had insignificant activity
(Table 3) The corresponding dithiol carbamate was com-
pletely inef~ective. Table 4 contains a further example of
the herbicidal action of the new isoxazolylmethylthiol
carbamatesO
2) Whereas prior art thiol carbamates can only be used in
specific crop plants or groups thereof (eOg., broadleaved
species) because of (a) their phytotoxicity, (b), incor-
poration necessary ~or herbicidal action~ and (c) the weed
spectrum combatted, some of the new compounds have an im-
proved and wider selectivity (Tables ~, 5, 6 and 7)~ Plant
physiology may provide an explanatio~ for the selectivity
.~
B~;~3
OOZ~ 32,106
of the compounds of the invention; the selectivity may also
be attributable in part to the application method employed.
Immobile substances distributed on the surface of the soil
do not come into contact in phytotoxic amounts with the
seeds and roots of the crop plants lying somewhat deeper.
This selectivity is apparent in the case of compounds which
can be left on the surface of the soil after application,
but does not exist when the active ingredients have to be
incorporated into the soil because of their high vapor
pressure or for other reasons, in order to avoid eva-
poration lossesO
3) The new compounds according to the invention had, when
incorporated before sowing, an action similar to that of
prior art compoundsO When applied without incorporation
they were superior to the prior art thiol carbamates suit-
able for the crop in question (Table 8)o Remarkable in
this connection is the fact that for instance the compound
3-methyl-5-isoxazolylmethyl-N,N-diisopropylthiol carbamate,
when applied preemergence to the surface, combatted un-
wanted plants in Indian corn just as well as significant
; prior art preemergence herbicides of different structure
(Table 9)O Successful control was also obtained during and
after emergence of the unwanted plants; the crop plants
remained unaffected (Tables 8~ lC)o
4) The phytotoxicity of the vapors of N,N-diisopropylthiol-
2,3,3-trichloroallyl carbamate for wild oats is known. This
was confirmed in model experiments. Of the new compounds,
' . .
- 26 -
133
0OZo 32,106
it was f`ound that for instance the substance 3-methyl-5-
isoxaæoly]methyl-N,N~diisopropylthiol carbamate had just as
aggressive an action on the crop plant oats in the directly
treated vessels as N,N-diisopropylthiol-2,3-dichloroallyl
carbamate ~r N,N-diisopropylthiol-2,3,3-trichloroallyl
carbamateO The plants in the untreated pots located in the
same glass cylinder remained undamaged by this new com-
pound, whereas plant growth in the case o~ the comparative
compound had suffered (Table ll)o Consequently, not enough
active ingredient had escaped from the directly treated
pots to cause damage, via the gas phase, to the neigh-
boring test plantsO The actual vapor pressure of 3-methyl-
; 5-isoxazolylmethyl-N,N-diisopropylthiol carbamate was
1.3 x 10 5 mbar at 20C, whereas that Or N,N-diisopropyl-
thiol-2,3-dichloroallyl carbamate at the same temperature
was 3.7 x 10 4 mbar.
It goes without saying that the experimental results dis-
cussed here are only examples of the reaction of numerous un-
wanted and crop plants from a wide variety of botanical
families. The application rates too can be varied beyond the
examples; they depend on the end to which they are applied
and on local conditions (site, plant size), and may for
instance vary from 0O1 to 10 kg of active ingredient per
hectareO
The particular advantage of this new group of isoxa~olyl-
methylthiol carbamates over prior art thiol carbamates is the
range of possible application methods.
- 27 -
1~3B~33
. .
O~Zo 32,106
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- 32a-
11i~8133
o.z. 32,106
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- 32b-
~108~33
O.Zv 32,106
Table 4 - Herbicidal action of new isoxazolylalkylthiol
carbamates in the greenhouse; pre and postemergence
applicat;on
Compound Appl.rate Method Test plants and % damage
no. kg/ha Cyperus Echinochloa Lolium
esculO crus galli multifl.
26 3.0 PRE - 90 90
3,0 POST 90 90 9
_
28 300 PRE - 90 7
3.0 POST 90 90 90
-- -- -- _ _ _
~ 29 3.0 PRE - 90 90
; 3.0 POST 70 90 50
, . -- -- _ _ _' 33 3.0 PRE - o O
.~ 3.0 POST O 90 50
38 3.0 PRE - go 30
3.0 POST 90 90 90
_
PRE = preemergence treatment
POST = postemergence treatment
O = no damage
~ 100 = complete destruction
:~ `
`,
. - 33 -
,~
.,
8~ 3 ~
O.Z. 32,106
Table 5 - Selective control of grassy weeds in beet with
various thiol carbamates in the open; preplant
incorporation
Basic molecule 2 / "
R 0
Substituents in the Compound Appl. Test plants and
compounds examined NoO rate % damage
kg~ha Beta Al.opecurus
R1 R2 R3 vulgaris myosuroides
_
2 200 5 95
16 2.0 0 75
3 2.0 5 80
400 0 65
13 4.0 0 5
~ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _
~ 9 4,0 50 70
_
~ 14 400 50 90
-- -- _ _ _ _
C3H7i C3H7i ClCl 2~0 0 30
CH2-C = C-Cl 400 0 80
prior art
C3H7nC3H7n C2H5 prior art 200 10 80
4.0 30 95
' 0 - no damage
100 - complete destruction
_ 34 _
8133
O.Z. 32,106
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11~8~33
O.Z. 32,106
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1~8133
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~1~8~33
O,Z, 32,106
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~8133
O,Z, 32,106
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8~33
0,Z 32,106
In view of the methods of application possible with thecompounds of the invention, they, or compositions containing
- them, may be used not only in the crops listed in the tables
: but also in a wide variety of other crops for combatting
unwanted plant growthO Application rates may be from 0.1 to
15 kg/ha and more, depending on the object to be combatted.
; Individual crop plants are listed below:
- 42
8133
0 . Z . 32, 106
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~ 8133
OoZ~ 32,106
td
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~ 8133
O~Z, 32,106
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- 46 --
:
.
~1~8~33
O.Z. 32,106
The new isoxazolylalkylthiol carbamates of the invention
may be mixed with numerous respresentatives Or other groups
; of herbicidal active ingredientsO Such combinations broaden
the spectrum of action and have in some cases synergistic
effects. The following compounds are examples of those which
can be mixed with the compounds of the invention:
8133
.
0, ~ . 32, 106
R
~N-C-C132Cl
R 0 ~ -
R Rl
P PY
~3 CH- C -. CH .
CH3 ~H3
C2H5
C2H5
~_ , 2 3
C2~15
2 5
~_ - CH -C-OC H
C2H5
~H 3 -~ ~
CH3 CH2-CH2-0CH3 ~;
C~3
.
.
- - 48 -
~8~33
O.Z. ~2 106
CH2-CH-CH2 CH2=CH-CH2-
Rl~ CH3
N-C-N
'
R Rl R2
CH
~HC~ H CH3.
CH3
H3CO~ H CH3
Cl
~ H CH
F3C
;~ H3C~ H CH3
C 1
C~3 :
C 14~ H C H- C- CH
Cl-~9-0~ H CH3
.
~N/>-- CH3 ` . H
~--N
/`S~ CH3 H
F3C
Br~3- H OCH3
C'- ~ H OCH3
.
' - 45 - .
O. Z, 32 106
R Rl R2
C l-Ç3 - H OCH 3
Cl
H 3co-~3 - H OCH 3
Cl
o
R~ N_
~ N;~ 2
R R~ R2
tert. CIlH9 IIH2 SCH3
~CH3
tert . C 4Hg -N - CH- CH SCH;
~9- NH2 3
O CH
" [~3
R
-CH~ . :
-N ~
/CH 3
-N~
C-CH
" 3
O
B:~33
O.Z. 32 106
R2 N02
Rl ~ N ~ 4
R N02
R Rl R2 R3 R4
CF3 H n.C3H7n.C3 7
CF3 H n.C3H7 CH2cH
H S2NH2 H n.C3H7 3 7
H CF~ H n.C3H7 CH2~ -
/C2H5
CH3 CH3 H H C2H5
H CF3 NH2 n.C3H7n.C3H7
X
. ~
NHRl
R-HN
' ` R Rl X
tert.C4H9 C2H5
C2H5 Cl
i-C3H7 ~ Cl
C2~5 C2H5 Cl
: CH3
C2H5 -C-CN Cl
CH3
- 51 -
- .
' .
llU~3133
O. Z, ~52 lC6
R Rl X
C~l 3 -
4 -C-CN Cl
C2H5 CH CH2 C 3 Cl
CH3
R
- CH3 CH3 ~ anion
R
H
CH3-CC12~,C~-ONa
CCl 3-- C-ONa
C l-Ç3 -N~ C~- C- O- C 2~ 5
C=O O
~Cl ~
CH 3 CH3
N- C'H- C-O- CH \
Cl 1= CH3
,, ~ .
-- 52 --
8133
o~ z~ 32 106
Bo~ and salts
Br
NC ~ OH and salts
I
Br
02N ~3-o-N-~H~ OH and salts
N02
r I /CH 3
HN~N-C-NH-CH2-CH~
O O CH3
O
Cl ~NJ~o,
N~
.H3C H
., .
O
H
/N2 0
Q
C4Hg sec
N02
02N-~-OH and salts
CI~H9 sec
.
- 53 -
ilS~8133
0, Z, 32 106
~3 N ~__ NH2
0 Cl
~ N}~CH 3
CF3 0 Cl
~-CII~ lmd sslts
H
-CH.~ and salts
CH3 H
3 :
~N ' 2
~N-CH~ and salts
H
~3 / 3
~NH-C--CH2-C-c C'~2
Cl
-- 54 -
C~ B13;~ o z ,2 o6
C 1 - ~ - CH2 - CH- C- O- CH .~
O ' .
" 3
C1
C l~ o _ ~3 - O C H C - O- C H ~ - C
3 ~3 ~ 3
' 3 C~ Cl
- .. ..
CH3 ~ Cl
OR C 3H ~n
' ~1~, C-NH-O-CH2-CH=CH~ :~
3 ~ land salts
C-OCH
" 3
O
R - H or Na
COOCH3
Cl ~Cl
Cl ~Cl
COOCU3
: - 55 -
'
~8~33
' O,Z, ~2 106
CO~H
Cl
~1 1 and scllts
Cl NHz
Cl~ O~CH?-C-OH and sa.lts or. esters
~
Cl
-O-CII2~C-OH and salts or esters
CJ.~O-(CH2)3-C-OH and salts or esters
O
Cl
O
N~C-CX2-0-S- NHCH
~ ,- 3
~ O O
. -
H3~
As-ONa
~0 0
Cl
Cl-~-0~~ 0-C~I- C-O-Na
O
Cl COOH
F3C ~~ ~-~2
:- ~ 56 ~ .
~'
.~, .
~)8 13;~
O.Z. 32,106
~ ,,
N-C-CH2-0-S-I~H ~ i-propyl
,, O O
~N-C-CH2-0-S-NH i-propy 1
O O
It is also useful to be able to apply the new compounds
according to the invention9 either alone or in combination
with other herbicides, in admixture with other crop protection --
agents, e.gO, agents for combatting pests and phytopathogenic
fungi, and growth regulatorsO The new compounds may also be
mixed with mineral fertilizer solutions used to overcome
nutritional or trace element deficienciesO
Application may be effected for instance in the form of
directly sprayable solutions, powders, suspensions (including
high-percentage aqueous, oily or other suspensions), disper-
sions, emulsions, oil dispersion, pastes, dusts, broadcasting
agents, or granules by spraying, atomizing, dusting, broad-
casting or wateringO The forms of application depend entirely
on the purpose for which the agents are being used; in any
case they should ensure a fine distribution of the active
ingredient.
For the preparation of solutions, emulsions, pastes and
oil dispersions to be sprayed direct, mineral oil fractions of
medium to high boiling point, such as kerosene or diesel oil,
further coal-tar oils, etcO and oils of vegetable or animal
origin, aliphatic, cyclic and aromatic hydrocarbons such as
` benzene, toluene, xylene, paraffin, tetrahydronaphthalene,
- 57 -
i~)813~
OOZ. 32,106
alkylated naphthalenes and their derivatives such as methanol,
ethanol, propanol, butanol, chloroform, carbon tetrachloride,
cyclohexanol, cyclohe~anone, chlorobenzene, isophorone, etc.,
and strongly polar solvents such as dimethylformamide, di-
methyl sulfoxide, N-methylpyrrolidone, water, etc. are suit-
ableO
Aqueous formulations may be prepared from emulsion con-
centrates, pastes, oil dispersions or wettable powders by
adding waterO To prepare emulsions, pastes and oil dispersions
: 10 the ingredients as such or dissolved in an oil or solvent may
be homogenized in water by means of wetting or dispersing
agents, adherents or emulsifiersO Concentrates which are
suitable for dilution with water may be prepared from active
ingredient, wetting agent, adherent, emulsifying or dispersing
agent and possibly solvent or oil.
Examples of surfactants are: alkali metal, alkaline earth
metal and ammonium salts of ligninsulfonic acid, naphthalene-
sulfonic acids, phenolsulfonic acids, alkylaryl sulfonates,
~ alkyl sulfates, and alkyl sulfonates, alkali metal and
: 20 alkaline earth metal salts of dibutylnaphthalenesulfonic acid,
lauryl ether sulfate, fatty alcohol sulfates, alkali metal
: and alkaline earth metal salts of fatty acids, salts of sul-
fated hexadecanols, heptadecanols, and octadecanols, salts of
sulfated fatty alcohol glycol ethers,condensation products of
sulfonated naphthalene and naphthalene derivatives with
formaldehyde, condensation products of naphthalene or naphtha-
lene or naphthalenesulfonic acids with phenol and formaldehyde,
polyoxyethylene octylphenol ethers,ethoxylated isooctylphenol,
- '
~D18133
OOZ. 32,106
ethoxylated octylphenol and ethoxylated nonylphenol, alkyl-
phenol polyglycol ethers, tributylphenol polyglycol ethers,
alkylaryl polyester alcoholsa isotridecyl alcohols, ratty
alcohol ethylene oxide condensates, ethoxylated castor oil,
polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene,
lauryl alcohol polyglycol ether acetal, sorbitol esters,
lignin, sulfite waste liquors and methyl cellulose.
Powders, dusts and broadcasting agents may be prepared
by mixing or grinding the active ingredients with a solid
carrier.
Granules, e.g., coated, impregnated or homogeneous gra-
nules, may be prepared by bonding the active ingredients to
solid carriers~ Examples of solid carriers are mineral earths
such as silicic acid, silica gels, silicates, talc, kaolin,
Attaclay, limestone, lime, chalk, bole, loess, clay, dolomite,
diatomaceous earth, calcium sulfate, magnesium sulfate,
magnesium oxide, ground plastics, fertilizers such as
ammonium sulfate, amrnonium phosphate, ammonium nitrate, and
ureas, and vegetable products such as grain flours, bark meal,
wood meal, and nutshell rneal, cellulosic powders, etc.
The formulations contain from 0.1 to 95, and preferably
` 0.5 to 90, % by weight of active ingredient.
There may be added to the compositions or individual
active ingredients (if desired, immediately before use (tank-
mix)) oils of various types, wetting agents or adherents,
herbicides, fungicides, nematocides, insecticides,
bactericides, trace elements, fertilizers, antifoams (e.g.,
silicones), growth regulators, antidotes and other
~ 59 -
33
O~ZO 32,106
herbicidally effective compounds~ The last-mentioned herbici-
dal compounds may also be applied before or after the
individual active ingredients according to the invention or
compositions thereof.
These agents may be added to the herbicides according to
the invention in a ratio by weight of from 1:10 to 10:1. The
same applies to oils, wetting agents and adherents, fungi-
cides, nematocides, insecticides, bactericides, antidotes and
growth regulatorsO
EXAMPLE 4
90 parts by weight of compound 1 is mixed with 10 parts
by weight of N-methyl-~-pyrrolidoneO A mixture is obtained
which is suitable for application in the form of very fine
dropsO
: EXAMPLE 5
20 parts by weight of compound 2 is dissolved in a mix-
: ture consisting of 80 parts by weight of xylene, 10 parts by
weight of the adduct of 8 to 10 moles o~ ethylene oxide to 1
mole of oleic acid-N-monoethanolamide~ 5 parts by weight of
the calcium salt of dodecylbenzenesulfonic acid, and 5 parts
by weight of the adduct of 40 moles of ethylene oxide to 1
mole of castor oilO ~y pouring the solution into 100,000 parts
by weight of water and uniformly distributing it therein, an
aqueous dispersion is obtained containing 0~02% by weight of
the active ingredient.
EXAMPLE 6
; 20 parts by weight of compound 3 is dissolved in a mix-
` ture consisting of 40 parts by weight of cyclohexanone,
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1108133
.
O~ZO 32,106
30 parts by weight of ;sobutanol, 20 parts by weight of the
adduct of 7 moles Or ethylene oxide to 1 mole of isooctyl-
phenol, and 10 parts by weight of the adduct of 40 moles of
ethylene oxide to 1 mole of castor oilO By pouring the
solution into 100,000 parts by weight of water and uniformly
distributing it therein, an aqueous dispersion is obtained
containing 0002% by weight of the active ingredientO
EXAMPLE 7
20 parts by weight of compound 4 is dissolved in a mix-
ture consisting of 25 parts by weight of cyclohexanol, 65
parts by weight of a mineral oil fraction having a boiling
point between 210 and 280C, and 10 parts by weight of the
adduct of 40 moles of ethylene oxide to 1 mole of castor oil.
By pouring the solution into 100,000 parts by weight of water
and uniformly distributing it therein, an aqueous dispersion
is obtained containing 0.02% by weight of the active
ingredient.
` EXAMPLE 8
20 parts by weight of compound 4 i.s well mixed with
3 parts by weight of the sodi.um salt of diisobutylnaphthalene-
~-sulfonic acid, 17 parts by weight of the sodium salt of a
ligninsulfonic acid obtained from a sulfite waste liquor, and
60 parts by weight of powdered silica gel, and triturated in
a hammer mill~ By uniformly distributing the mixture in
20,000 parts by weight of water, a spray liquid is obtained
containing 0.1% by weight of the active ingredient.
. EXAMPLE 9
3 parts by weight of compound 4 is intimately mixed with
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O.Z. 32,106
97 parts by weight of particulare kaolin. A dust is obtained
containing 3% by weight of the active ingredient.
EXAMPL,E 10
30 parts by weight of compound 4 is intimately mixed
with a mixture consisting of 92 parts by weight of powdered
silica gel and 8 parts by weight of paraffin oil which has
been sprayed onto the surface of this silica gelO A
formulation of the active ingredient is obtained having good
adherence
EXAMPLE 11
40 parts by weight of compound 5 is intimately mixed
with 10 parts of the sodium salt of a phenolsulfonic acid-
urea-formaldehyde condensate, 2 parts of silica gel and 48
parts of waterO Dilution in 100,000 parts by weight of water
gives an aqueous dispersion containing 0004 wt% of active
ingredientO
EXAMPLE 12
; 20 parts of compound 6 is intimately mixed with 2 parts
of the calcium salt of dodecylbenzenesulfonic acid, 8 parts of
a fatty alcohol polyglycol ether, 2 parts of the sodium salt
of a phenolsulfonic acid-urea-formaldehyde condensate and
68 parts of a paraffinic mineral oil. A stable oily dispersion
is obtained.
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