Note: Descriptions are shown in the official language in which they were submitted.
~5~
The present invention rela-tes to oxime carbamates and oxime
carbonates of the general formula I
Ar - C - CN
: 11 ~I),
N-O-C0-R
to novel compositions based on these compounds, and to the application
of these compositions or compounds for the protection of cultivated plants
against harmful agricultural chemicals.
The symbols in the formula I have the following meanings:
in which Ar is a phenyl group of the formula
R3 ~ ~
a naphthyl group which is substituted by R2 and R3, or a thiophene
ring which is unsubstituted or substituted by halogen or lower
- alkyl, R2 and R3 independently of one another are hydrogen, halogen,
. N02, lower alkyl, C~3, methoxy or ethoxy, and R is either
; a) radical -N(R5)~R6), in which R5 is hydrogen, lower alkyl or lower
: alkoxy, R6 is an aliphatic group, or a phenyl group which is
unsubstituted or substituted by halogen, lower alkyl, C~3, methoxy
or ethoxy, or
b) radical -YR6, in which Y is oxygen or sulfur and R6 is as defined above.
.~
- . .
., . ,
: :.,
~S9~7~
, - 2 -
.
:,
Co~pounds of the formula I are accordingly a~ carbamates or
b) ~thio) carbonates.
Halogen in the formula I is -fluorine, chlorine, bromine or
iodine.
The term 'alkyl' on its own or as part of a substituent includes
branched and unbranched Cl to C8 alkyl groups; lower alkyl denotes Cl-C~ alkyl.
Examples are methyl, ethyl, propyl~ isopropyl, butyl, isobutyl, sec-butyl
and tert-outyl, and also the higher homologues amyl, isoamyl, hexyl,
heptyl or oc~yl, together with isomers thereof.
The term 'alipha~ic group' includes radicals which are saturated
~alkyls) and also unsaturated ~alkenyls, alkadienyls or alkynyls), which are
halogen-substituted, cyano-substituted and interrupted by oxygen, and
which contain a maximum of 8 carbon atoms. The term 'aromatic group'
in the deinition o the substituents R5 and R6 embraces phenyl and naphthy].
~ I
r,
;`~
':
' :
~;9(~71
The ~erm 'araliphatlc radical' is to be interpreted in accordance with
the two preceding definitions. An araliphatic radical includes an aryl
group such as unsubstituted or mono- to tri- substituted phenyl, or naphthyl,
which is bound by way of lower alkyl or lower alkenyl to the radical of the
molecule. Examples are benzyl, phenethyl or phenylallyl and also homologues.
The arylglyoxylnitrile oximes of tihe general formula
- C=N-OH
(X = H, Cl, Br, NO2),
Xn C_N
., ~.
suggested in the United States Patent Specification No. 3,799,757, are
insufficiently effective as growth inhibitors and plant-growth regulators;
furthermore, they are not stable and decompose after a fairly short space
oE time. No herbicidal-antidote action has become known.
In comparison with the above compounds, oximes of the formula
I are excellently suitable for protecting cultivated plants, such as
cultivated millet, rice, maize, varieties of cereals (wh~at, rye, barley
,
7~
'
:~
;
or oats), cotto~, sugar beet, sugar cane, soya bean, etc., from being
attacked by agricultural chemicals harmful to plants, particularly by
herbicides of the most varied classes of substances, such as ~riazines,
,
~! phenylurea derivatives, carbamates, thiolcarbamates, haloacetanilides,
halophenoxyacetic acid esters, substituted phenoxyphenoxyacetates and
phenoxyphenoxypropionates, substituted pyridineoxyphenoxyacetates and
~' pyridineox~yphenoxypropionates, benzoic acid derivatives, and so forth9
in cases where these chemicals do not act seleetively or do not act sufficiently
selectively, that is to say, damage to a greater or lesser extent the cultivated
plants in addition to destroying the weeds to be controlled. The invention
relates also to compositions which contain these oxime derivatives of the
, formula I, together with herbicides.
.,;,
~i '
. ~ .',1.
. ~ .
, . .
. ~ .
~5~
There have already been suggested as antidotes various
substances able to speciEically antagonise the harmful
action of a herbicide on the cultivated plant, that is
to say, able to protect the cultivated plant without
noticeably affecting the herbicidal action against the
weeds to be controlled. Depending on its properties,
an antidote of this kind (also called a safener) can be
used for the preliminary treatment of the seed of the
cultivated plant (dressing of the seed or of the seed-
lings); or it can be applied into the seed furrows before
sowing; or it can be applied as a tank mixture, on its
own or together with the herbicide, before or after
emergence of the plants. The pre-emergence treatment
includes both the treatment of the cultivated area
before sowing (ppi - pre plant incorporation) and the
treatment of the sown cultivated area before emergence
o the plants.
Thus, the British Patent Specificat:ion No. 1,277,557
describes the treatment of seed and seedlings of wheat
and sorghumwith certain esters and amides of oxamic acid
before the attack by N-methoxyme~hyl-2',6'-diethyl-
chloroacetanilide (Alachlor). Other publications (German
Offenlegungsschriften Nos. 1,952,91() and 2,245,4719 and
~rench Patent Specification No. 2,021,611) suggest anti-
dotes for the treatment of cereals, maize seed and rice
seed to protect them against attack from herbicidal
thiolcarbamates. In the &erman Patent Specification No.
1,576,676 and U.S. Patent Specification No. 3,131,509,
hydroxyaminoacetanilides and hydantoins are suggested
for the protection of cereal seeds against carbamates,
such as IPC, CIPC, and so forth. In further development,
however~ all these preparations have proved to be
inadequate.
,,, , , _, .. . . . .. _ . _ ., .. ... _ _ _. _ _ . _ . ... . _ .. .. _ . _ . _ .. . _ -- --_ .. _ _ . .. .... ___ .. _ _ .. --.. ~-- -- .
--- _ _ _ -- --.--~ -- -- -- -- -- ---- - -- - - ~a~--
.. ~ . . .
.
,
~59~'7:1L
- 6 -
To be emphasised as antidotes are in particular those compounds
of the formula I in which Ar is a phenyl or naphthyl radical as defined
in the foregoing, and the other substituents have the following meanings:
R2 and R3 independently of one another are hydrogen, halogen, and lower
alkyl, methoxy or ethoxy, whilst Y and R5, and R6 have the meanings already
defined. This subgroup is to be called compound group Ia.
Amongst these compounds of the group Ia, the g~oup Ib constitutes
one of the compound groups preferred as antidotes. Compounds of the group
Ib are those of the formula I in which Ar is a phenyl group as defîned in
the foregoing, R2 and R3 are hydrogen, halogen, lower alkyl, CF3, methoxy
or ethoxy, R5 is hydrogen7 lower alkyl or lower alkoxy, R6 is an aliphatic
group1 or a phenyl group which is unsubstituted or substituted by halogen,
lower alkyl, CF3, methoxy or ethoxy, and Y is oxygen or sulfur.
An important group of antidotes is -formed by those compounds of
the formula I in which Ar is a thiophene ring unsubstituted or substituted
by halogen or lower alkyl, and in which the substituents Y, R5, R6 and R7
have the meanings given for the compound group la, but preferably the
meanings given for the compound group Ib.
.,
' '
'
~ ; 3 -~
.~ . , - . , , :, , ,, .. ~ . ,
: ~ . , :; : ;,: , . ~ , . :
37~
-- 7 --
SurprisinglyJ oximes of the formula I have the property of
being able to protect cultivated plants against attack from agricultural
- chemicals harmful to plants, particularly against herbicides of the most
varied classes of substances, including 1,3,5-triazines, 1,2,4-triazinones,
phenylurea derivatives, carbamates, thiolcarbamates, phenoxyacetates,
phenoxypropionates~ haloacetanilides, halophenoxyacetates, substituted
.: .
phenoxyphenoxyacetates and phenoxyphenoxypropionates, substituted pyrid-
inephenoxyace*ates and pyridinephenoxypropionates, benzoic acid derivatives,
and so forth, in cases where these chemicals are not compatible, or not
, lO sufficiently compatible, with the cultivated plants.
Depending on the purpose of application, swch an antidote of the
formula I can be used for pretreatment of the seed of the cultivated
plant (dressing of the seed or of the seedlings), or can be applied to the
soil before or after sowing, or can be applied on its own or together with
the herbicide before or after emergence of the plants. The treatment of
the plant or of the seed with the antidote can therefore be carried
out essentially independently of the point of time of application of the
.~
. ~
, '
:,
~ 7
-- 8 --
phytotoxic chemicals. It can however be carried out
also simultaneously (tank mixture). Pre-emergence
treatment includes both the treatment of the cul~ivated
area before sowing (ppi = pre pIant incorporation) and
the treatment of the sown area before emergence of
the plants.
The applied amounts of the antidote in proportion
to the amounts of herbicide depend largely on the type
of application. If a field treatment is undertaken, the
amounts of antidote of the formula I with respect to
amounts of the phytotoxic chemical are in the ratio of
1:100 to 5:1, preferably 1:20 to 1:1~ In the case of
seed dressing and similar specific protective measures,
much smaller amounts of antidote are required however
compared with the amounts of herbicide employed for
example later per hectare of cultivated area (for example
about 1:3000 to 1:1000). There is as a rule only a loose
connection between protective measures, such as seed
dressing with an antidote of the formula I, and a possible
subsequent field treatment with agricultural chemicals.
Pretreated seed and plant material can later come into
contact, in agriculture, hor~iculture and forestry, with
a variety of chemicals.
The invention relates therefore also to compositions
for protecting cultivated plants, which compositions
contain as active substance an antidote of the formula I
together with customary carriers. Compositions of this
type can optionally be additionally mixed with those
agricultural chemicals having an effect from which the
cultivated plant is to be protected, for example they
can be mixed with a herbicide.
Within the scope of the present invention, cultivated
plants are all plants which produce in some form useful
.: .
~ -. ~ . .:
, .
.
,
~ ~ S9 071
_ 9 _
materials (seeds, roots, stalks, tubers, leaves, blossom,
and components such as oils, sugar, starch, protein,
and so forth), and which are cultivated and attended to
for this purpose. These plants include for example all
varieties of cereals, maize, rice, cultivated millet,
soya bean, beans, peas, potatoes, vegetables, cotton,
sugar beetl sugar cane, peanuts, tobacco and hops, and
also ornamental plants, fruit trees as well as banana,
cocoa ancl natural rubber plants.-This list of plant types
~oes not constitute any limitation. An antidote can
as a rule be used everywhere where a cultivated plant
has to be protected against the phytotoxicity of a
chemical.
~,
Compounds of the formula can be produced from the free
~- oximes by several processes, which are shown in schematic
: form in the following:
,. . .
,. ~. .
..
\
:' ' .
.~
.' :
.~ . . .
- . . :
. . . . .
a) Carbamat e s
Ar ~
/ C=NOH + O=CaN -R6 ~ C----NO -CO -NHR6
X X
Ar Ar
\ C=NO-Na + Cl-CO-N-R6~ / C-NO-CO-NR6
X ~ X R
" .
Ar ~r
\
/ C=NO-CO-Cl ~ NH2R6 ~ C=NV-CO-NHR6
X X
.j
.,
b) h~o) carbonates
.
' Ar
C=NO-Na ~ Cl-CO YR7 ~ C=NO-CO-YR7
.' X X ;~
Ar .Ar
\ \
G-NO -CO -Cl + HO - R7~ C=NO -CO -OR7
X , X
; .
Ar . Ar
;; C=NO-CO-Cl + Na-S-R ~ \C=NO-CO-SR
I ~ 7 , 7
~ .
Y ~.
'
: . ., , ,: " .
- ,
: ,:,:
~, ,A~L 5~
(In the preceding diagrams, Na represents sodium
or another alkali metal).
ISuitable for obtaining compounds of the formula I
; are essentially all solvents which behave inertly under
the conditions of the reaction. For example, hydrocarbons,
particularly however polar solvents such as acetonitrile,
dioxane, cellosolve or DMF, and also l~etones such as
methyl ethyl ketone, acetone, and so :Eorth. Solvents
containing hydroxyl groups are excluded.
The temperatures are within the range of -10C to
abou~ 150C, preferably between 20 and 120C.
; As agents splitting off hydrogen halide, it is
possible to use bases, such as tert. amines (triethylamine,
triethylenediamine, piperidine, and so for~h). Also a
suspension of sodium carbonate in an anhydrous reaction
medium suffices in some cases. Oximes are present in two
stereoisomeric forms, the syn and anti form. By 'compounds
of the formula I' are accordingly meant, within the
scope of the present specification, both stereoisomeric
; forms, on their own or as mixtures with each other in
any reci.procal mixture ratio.
The Examples which follow illustrate the production
of the novel oximes of the formula I. Temperature values
are given in degrees Centigrade.
' ' ' , ~ :
. . .
~5~7~L
- 12 -
Example l
,
,~ Production of ~ C-CN [Comp. 1}
N 0-C0-NHCH3
23.5 g (0.16 mol) of benzyl cyanide oxime is placed
into 100 ml of acetonitrile. After 25 ml of methyl-
isocyanate and a small, catalytically acting, amount
of diazabicyclooctane have been added, the reaction
mixture is heated to 50C~ and the final product precipi-
tates after a short period of time. It is allowed to
i stand overnight, and is then filtered off with suction,
washed with acetonitrile, and subsequently dried at 60
with hexane to yield 29.2 g (= 89.8 % of theory~ of final
product having a melting point of 172-175C.
Example 2
Production of ~ C-CN 3 [Comp. 53
N-0-C0-NH - ~
;. ' , .
14.6 g (0.1 mol) of benzyl cyanide oxime is placed
into 100 ml of acetonitrile; thexe are then added 18.7 g
(0.1 mol) of 3-trifluoromethylphenylisocyanate and a~
catalytically acting, small amount of diazabicyclooctane.
l~ The reaction commences immediately, whereupon the reaction
;- mixture heats up to about 50. It is stirred on a water
bath for a further 4 hours 3 the final product which has
precipitated is then filtered of~ with suction, washed
~` with acetonitrile, and dried in vacuo at 50 to yield
25.5 g of final product having melting point o~ 172-173.
, . :
,1 ~ ' ' .
. . '.
- 13 - ~ ~ 5
Example 3
Production of Cl ~ C-CN IComp. 379]
Cl N-0-C0-S C2H5
6.3 g (0.05 mole) of chlorothioformic acid-S-ethyl
ester is added dropwise to a mixture of 11.9 g (0.05 mole)
of the sodi~m salt of 3,4-dichlorobenzyl cyanide oxime
in 50 ml of acetonitrile. The reaction mixture i5 then
heated, refluxed for 4 hours and concentrated in vacuo.
Methylene chloride is added to the residue, and the
mixture is stirred with active charcoal and filtered.
The filtrate is concentrated by evaporation to yield
11.2 g (= 73.7 % of theory) of the final product in the
form of oil.
Example 4
H C200C-C-CN
Production of 5 ~9 ~ [Comp. 138]
N-0-C0-NH ~ Cl
' '' `` ' .
14,2 g (0.1 mol~ of cyanoacetic acid ethyl ester oxime
is placed into 100 ml of acetonitrile in a flask fitted
with stirrer. A solution of 15.3 g of p-chlorophenyl-
isocyanate in 20 ml of acetonitrile is added dropwise
with stirring, and the reac~ion mixture is stirred for
5 hour~ at 60-70~ The solution is afterwards filtered
hot and the filtrate is cooled in ice water. The final
product which has crystallised out is filtered off,
washed with acetonitrile/hexane and dried~ i~ has a melting
point of 147-148C.
. ;
~ 14 - ~ 5~
.. . .
In this manner or by one of.the aforementioned methods,
; there can be produced the following carbamates of the
, - formula:
g~ l
2 ~ C - C~
. N-O-CO-N-R5
R6
Comp. Rl R2 R5 ~6 Physical
- NQ. constants
~ , _ . ... . . ...... ..
1 H H H CH3 m.p. 172-175
~ H H H C2H5 m.p. 93-96
3 H H H n-C3H7 m.p. 39-91
4 H H H isoC3H7 m.p. 92-94
H H H n-C4H9 m.p. 98-101
~ H H H ter~.C4H9 solid
7 H H H 2C~l2-cl m.p. 138-141
~ H H H -CH2-0-CH3
9 H H H ~
lV H 4-Cl H n-C4H9 m.p. 124--126
1i H 4~Cl H CH2 ~ CH3 m.p. llo ~14
12 H 4-Cl H tert.C4H9 m.p. 102-~105
13. H 4-Cl H isoC3H7 m.p. 140 144
14 H 4-Cl H CH3 m.p. l91 L93
H 4-Cl H ~2H5 m.p. lO5-108
16 ~ 4-Cl ~I nc3H7 m.p. 112-113
. ,:
. , ~ , . ~
.
- 15 ~
Comp. R R . R R Physical
No. 1 2 5 6 constants
i ~ . 17 2-C1 4-Cl H CH3 m.p. 152-154
:; 1 18 2-C1 4-Cl H CH3 m.p. 124-128
19 3-C1 4 Cl Htert . C4H9 solid
- . . 20 H 4 -Br CH3 CH3 m . p . 113 -115
21 2 -Cl 4-Cl . H isoC3H7 m . p . 92 -93
:22 ~ 4-Cl . C~I3~H3 m.p.. 131-132
23 Z-Cl 4-Cl ~H3 CH3 solid
24 4-t.C4H9 H H CH3 m.p. 162-165
: . 25 4 -t . C4H9 H ~I C2H5 solid
26 4-t . C4Hg H H nc3H7 solid
27 4 -t . C4Hg H Htert . C4H9 oil
28 H 4-CH30 H H
29 H . 4-CH30 H CH3 m.p.182-184
H 4 CH30 H C2H5 m.p.106-110
31 H 4-CH30 H isoC3H7 m.p.129-131
32 H 4 ~ (CH3~2N ~ H CH3
33 H 4-C2H50 H CH3
34 H 4-C2H50 H isoC3H7
H 4-N02 H (:H3
36 ~ 3-CF3 H CH3 m.p. 150 151
37 H 3~CF3 H C;~I5
38 ~ 3-C:F3 H H
39 lH 3-CF3 CH3 CH3
.~ 40 H H G2H5C2H5 oil
41 H 3-~F3 H nC4H9
.~ 42 H H H -C6H5 m . p . 132 134
b~3 ~ H H H-C6~4Cl(4) m.p.18b~-186
44 H H ~I -C~,H4-CH3(4~ m-p.153-154
H 4-t.C4H9 H -C H m.p. 131-133
46 3-C1 4-Cl H -C6H4C1(4)
47 3-Cl `4 Cl H -C6H~C12(3,4) m.p. 210-213
.
:: .......... .
.
- 16 3~ 7~
Comp. Rl R~ R5 R6 Physical
No. constants
,: . _.
4~ 3-C1 4-Cl H -C6H3C1~3) isoC3H7 ~4) m.p- 172 175
49 H H H -(6H4-~F3(4) m.p. 188-190
H H H -C6H3C1 ( 3) CF3 (4) m . p . 207 -208
51 H H H -C6H3(CF3)2(3,5) m.p. 196-198
52 H H C6 4 F(4) rn.p. 159-161
53 H H H -C6H4-CF3(3) m.p. 172-173
54 H 4-Cl X -C6H4-CF3(3) m.p. 187-190
H 4-Cl H -C6H4Cl(4) m.p.204-205
56 H 4-C:1 H -C6H3C12(3,4) m.p.204-205
57 H 4-~:1 H -C6H3Cl(3)isoC3H7(4) m.p. 150-151
58 H 4-Cl H -C6H5 mOp. 148-150
59 2 -Cl 4-Cl H -C~j,H3C12 (3, 5) solid
60 4-t.C4H9 H H -C~H4C1(4) mOp.131-133
C4Hg H H ~C6H3C12~3~4) m.p.6 8 -71
62 4-t~C4Hg H H -C6H3(C@3)2(3,5) m.p.58 60
63 H 3-CF3 H -C~,H4(CF3) (3)
64 H 3-CF3 H -C6H4(CF3) ( )
H 4 -CH30 H -C6H3C12 ( 3 ~ 4)
66 H 4 C2H5 -C6H4-CF3(3)
67 H 3 CF3 H -C6H5 m.p. 141-143
68 H 3 C:F3 H -isoC3H7 ~ p- 116-118
~9 2~C1 4-Cl H C6H5 m.p. 163-164
2-C1 4-Cl H -C6H3tCF3)2(3~5) m.p. 110~113
71 2~C1 4lCl H -C6H3C12(~,4) m.p. 152-153
72 4-t.C4~ H H -C6H4(CF3)(3) m.p. 136-140'
.
.
- : . . . . : i .
. ~ . . . .
.~
,
,
: ~ 5~ ~7
- 17 -
- -and also following carbamates Qf the formula:
,
I ~
- ~ ~ R5
R6
Comp, X Rl R2 R5 R6 Physical
No. constants
73 CH3 H H H OEI3 m~p. 97-99
74 COC~ H H H CH3
H 2-C1 4-Cl H C~13 m.p. 137
76 H ~ H H CH3 m.p.. 92-94
77 H H 4-Cl H C~13 m.p. 133-136
78 H H 4-(CH3)2N H CH3
79 CH3 H 4-(C2H5)2N H CH3
~13 3-N02 H H CH3
81 H 3-CF3 H H CH3
82 -COO~H5 3-CF3 H H ~13
83 H 4-CH30 H CH3
84 ~13 4-CH30 H H ~H3
85 H 3-N02 H H CH3
86 H 2-N02 H H C~I3
87 -COCH3 H H H -C6H3C12(3 9 4)
8B -COCH3 H H H -C6H3(CH3)2(2,4)
89 H H H H -C6H4C1~4) m.p. 145-146
90~ H 2~C1 6-Cl H -C6H4cl(43 m.p. 142-144
91 CH3 H ~ H -C6~I4Cl(4) m.p. 105-106
92 -COCH3 H H H -C6H4cl(4) m.p, 297-298o
93 H H 4-Cl H -C6H4Cl(4) m.p. 151-152
94 H H 4-Cl H ~C6H5 m.p. 106-109
.~ , "
~. . . .
:. ,-
.
.
,:~
. .
.
- 18 -
Comp. X Rl R2 R5 R6 constants
.. . . _ . . , _
95 H H 4-Ci H 6 4 CH3(3) m.p.llg_l2l0
96 H H 4-Cl H ~C6H4-F(4) m.p~l30-132
97 H ~ 4-Cl H -C6H~No2(4)
g8 -COOC2H5 H H H CH3
99 -COOCH3 H H H CH3
100 -COOt.~H9 H H H ~H3
101 ~COOCH3 H 4-Br H ~H3
102 -COOC2H5 H 3-CF3 H 3
103 -COOCH3 H 4-Cl H -C6HS
104 -CONHCH3 H H H CH3
105 -CONH2 H H H CH3
106 -CONHisoC3H7 H H H CH3
107 -CONHCH3 H 4-CH~ H CH3
108 -CONHCH3 H 4-Cl CH3 CH3
109 -CONHisoC4H9 H H H CH3
llo -CONHt.C4Hg H 4-Cl H CH3
.
~,
.
,, , ' ~
: ` , :, , .~
' ' ' , ' '
'.
L5~37~L
:
and also following carbamates of ~he formula
:' ' '
Ar - C - X
N~0-C0-N-R5
R6
. .
Comp. Ar ~ ~5 R6 Physical
No. constants
111 ~ -CN ~ c~3 m.p.l54-158
112 ~ -CNC2H5C2HS m.p.162-164
113 ~-naphthyl CN H tert.C4H9
114 ~-naphthyI -CN H isoC3H7
115 ~-naphthyl -CN H -C6H4C1(4)
116 2-furanyl -CN H CH3
117 2-furanyl -CN H -CH -C-CH
118 2-furanyl -CN H C6H3C12(3,4)
119 2-thienyl -CN H ~H3
120 2-thienyl ~CN H C2H5
121 2~thienyl -CH3 H ~H3
122 ~p)C6H5 0-C6H4 N2 3
123 ~p)C6H5-0 C6H4- -COCH3 H -C~H~CF3(4)
124 H2N-C0- -CN H -C6H4Cl(3) m.p.203-2040
125 H2N-C0- -CN H ~C6H4Cl(4) m.p. 201-203
126 ~2N-CO- -CN H -~6H3C12(2,5~ m.p,176-177
127 H2NVC0- -CN ~ -C6H4cF3(2~ m.p. 179-183
128 H2N-C0- -CN H -C6H4CF3(4) m.p.l7o-l8oo
129 ~2N-CO_ -CN ~ ~c6H3cl(3)cH~4)m~p~l63-
130 ~ ~2N-CO- -CN H CH3 m.p.176-177
,
.
,. . . , , , , , ~;, ~ .; ,... . .
- . . : . :
.. . . - , . ,. . ,, , :
~: :- . . ... : .- .
~L~5~7~1L
- 2~ -
Comp. Ar X R5 R6 Physîcal
. constants
_ _ .
H2 C0 -CN HC2H5 m.p.L].6-120
132 H2N-C0- -CN H -~l2C~2-Cl m-p.141-142
133 H~N-C0- -CN H -nC3H7 m.p.ll3-116
134 H2N-C0- -CN H -isoC3H7 m.p.125-126
135 H2N C0 -CN H -nC4H9 m.p,92~960
136 H2N-C0- -CN H -C6H5 m.p.174-175
137 H2N-C0- -CNH.-C6H3CF3(3)C1(4) m.p.182-
183
138 C2H500C- -CN H -C6H4C1(4) m.p.147-148
3 2 5 C CN H ~H3 m.p.101-103
140 2-thienyl -CN H -C~H3C12(3,4) oil
141 (5C1)2-thienyl -CN H CH3 m.p. 186
142 (5Cl)2-thienyl -CN H -C6H4C1~4) m.p. 186
143 (SCl)2-thienyl -CN H -C6H3C1(4)CF3(3) m.p.l84
.
,~ .
- - -
- : :
21 ~5~7~
and also following carbamates of the formula:
.
O
Il -
R - 0 C - C - CN
0 j ~5
N - 0 - C - N
R~
Comp. R~ R5- R6 Physical
No. ` constants
144 6 3CF3(3)Cl(4) m.p. 162-163
145 CH30- H C6H4CF3(3) m.p. :L47-148
146 CH30 H C6H5 m.p. 149 150
147 CM30- H C6H4N02(3) m.p. :L66-167
148 3 C6H4Cl(3) m.p. 'l62-163
149 CH30- H C6H4Cl(4) m.p. 157-158
150 CH30- H C ~4C1~2) m.p. 136-138
151 CH30- H C6H~CF3(4) m.p. 727-128
152 CH30- H C~H4(0C4~L9(i))(4) m.p. 139-140
153 CH30- H C6H3C12(3,4) m.p.l62-163ldecomp.
154 CH30- H C~H3Cl(3)Br(4) m.p.l70-171
155 ~H30- H C6H3C12(2,5) m.p.l64-165
156 CH30- H C6H3CH3t~)Cl(3) m.p.ll8-120
157 GH30- H C6H3CH3(2)C1(4) m.p.ll9-120
158 CH30-- H C6H3Br(2)CH3(4) m.p.l34-135
159 CH30- H C6~3(CH3)2(2~4) m.p. 115-117
160 CH30- H C6H3C1(2)N02~4) m.p.l65-166
decomp.
161 CH30- H C6H3C12(2l4) m.p.l43-145
162 ~ 0- H ~CH m~p. 122-123
163 CH30- H ~CH2CH2Cl m.p. 72-74
, . . .
i. . .
~ 7
- 22 -
Comp. R4 R5 R6 Physical
constants
164 2 5 6 5 m.p. 130-132
165 2 5 H -C~H4Cl(2~ m.p. 81 82
166 C2HS- 6 4 ( ) m.p. 139-141
167 C H o H -C6H~Cl(4) m.p. 156-157
168C2H5 0 H -C6~4CF3(3~ m.p. 117-119
169 2 5 6 4CF3(4) m.pO 136-137
170 2 5 6 4 2( ) m.p. 145-147
171 ~2H5-~ 6 4 3(4) m.p. 121-122
172 2 5 H ~C6H4(~-C4Hg(i))(4)m~p~ 127-128
173 C2 5 H -C6H3C12(3,4) m.p. 160-161
174 ~2 5 H -C6H3C12(2,5) m.p. 136-137
175 C2 5 H -~6H3CF3(3)C1(4) m.p. 141-142
176 ~2 5 H -~6H3C1(2)N02(4) m.p. 133-134
177C2H5 0 ~H3~C~3)2(3,5) m-p. 155-157
178 2 5 ~ -C6H3CH3(2)C1(4) m.p. 90-91
179C2H5 -0 H -C6H2C13 ( Z,4,5) m p 137 -139
180C2H5 0 H -~H3 m~p. 104-106
181C2H5 0 H CH2C12 m.p. 73-7S
182(~)~4Hg-0 H -C6H4C1(4) m.p. 128-130
183~s ) C~H 9 -0 H -C6H4 CF3 (3) m p 93 _ 95
184(s)C4Hg-O H -C6H~CF3(4) m.p. 109-110
185(s)C4H9-0 H -~6H3C12(3,4) m.p. 140-141
186(s ~ C4Hg-O H -~H3Cl~ (2,5) m . p . 100-101
187( s3C4Hg~O H -C6H3CF3~3)C1(4) m.p. 126-127
~8(s ) C4Hg-O ~ CH3 m.p . 80-81
189(~ ) C4H9-0 H -~H2CH2Cl m.p . 57 -59
190 CH2=CH -CH2 o H C6H5 m . p . 103 - 105
' '
~ , .
, " " . ' ' .
,' . ,
" ; ' ~, , " .
~L~5~
- 23 - .
Comp. R4 R5 6 Physical
No. constants
191 CH =CH-CH2-0 H C6H4C1(3) m.p. 118-120
192 CH2=CH-CH2-0 H C6H4C1(4) m.p. 131-132
193 CH2=CH-CH2-0 H C6H4CF3(3) m.P-106 107
194 CH~=CH-CH2-0 H C ~ 4CF3(4) m.p.l21-123
195 CH2-CH-CH2-0 ~ C6H3C12(3~4) m~p.l26-l27o
196 C~12=CH-CH2-0 H C6H3C12(2,5) m.p.l30-l3lo
197 CH~=CH-CH2-0 H C6H2C13(2,4,~ m~p.l24-l26o
198 CH2=CH CH2-0 H -C~2CH2Cl m.p.61-63
199 ~ _~_ H ~C6H4C1(4) m.p.141-142
200 ~ 0- H -C6H4CF3(3) m.p.94-96
281 ~ 0- H -C ~ 4Cl(4) m.p.162-163
20~ ~ ~ H ~~6H3cF3(~c~ )m~p~l3l-l32o
203 ~ 0_ H -C6H2C13(2,4,~ m.p.l24-12
204 ~ O-- H -~13 m. p~9-101
C H
205 CH~ CH20- H -C6H4C1(3) m.p. 136(decomp.)
(~6H5
206 CH=CH-CH20- H oC6~3C12(3,4)m.p.l38(decomp.)
C6H5
207 CH~CH-CH20- H -C6HzC13(2,4,5)m,p. 161(decomp.)
207a C~130- C~3 C~13 m.p. 105-106
. .
.
' ' ' ' .
. : ` ,:,, ~ ' ~'.;
- 24 - 1~5~6~7~
Comp. R4 R5 R6 Physical
constants
208 CH30 H C6H3C12(3,5) m.p. 156 tdecomp.)
209 <~} O - H C6H3C12t3,5) m.p.. 107 108
210 <~_ O - H C6H3C12(3,4) m.p. 162 163
211 CH30- H C6H3C12t3,4) m.p. 162-163;
.
' - ' ' .
,
- . __
~ `
~
~S~7
- 25 -
and also folIowing carbamates of ~he ~ormula
I CN
R N-C-C ~
10 ~ 'l 0 ~ R5
~6
Comp- Rs R6 R9 ~10 Physical
No. constants
- 212 H C6H3C12(3,4) -CH3 -~H3 m.p. 153-154
213 H C6H3CF3(3)Cl(4) CH3 -OE13 m.p. 154-156
214 H C6H5 ~ m.p. 143-144
215 H C6H4Cl(2) ~ m.p.120-123
21~ H C6H4C1(4) ~ m.p.142-144.
217 ~ C6H4CF3(4) ~ m.p.l60-162
~\
. 21g H C6H3C12~3,4) ~ m.p.153-154
, j /--\
219 H C6H4CH3(4) ~ m.p.133-135
220 H C6H3~F3(3)Cl(4) ~ m~p.l4Q~ (decomp.)
221 H C~H3~1t2)N02(4~ ~ m.p.l65(decomp.).
.
222 H C6H2C13(2~4~5) ~ m.p.~l43-145
: 223 ~ ~ 3 m.p.113(decomp.)
.
,, . . ~
.: , . . . :: :: :: .. : :
~5~7
- ~6 -
Comp, R5 R6 Rg Rlo Physical
o. constants
:
~ 224 H C6H5 ~ m.p. 124-125
~'
225 H C6H4C1(4) ~ m.p. 125-127
~~
226 H C6H3C12~3.4) ~ m.p. 155 157
--i
227 H C6H3CF3(3)Cl(4) ~ m.p. 145(decomp.)
228H -CH3 ~r~ m.p.,90(decomp.)
2~93 7 CH3 CH3 m.p. 46-50
230H CH(CH3)2 C~3 ~H3 m.p. 62-66
231H C4Hg CH3 CH3 oil
232C?H5 ~3 CH3 m.p. 90
233 H CH(CH3)2 H H m.p. 206-207
,
234 H CH3 CH3 CH3 m.p. 72-76
235 H CH2CH2Cl ~H3 CH3~ m.p. 99-101
.. ~ .
' 236 H C6H4C1(3) ~ m.p.l59-161
.,~. ~~
237 H C6H4CF3(3) 0 m.p.l30-132
~ , r~
238 N C6H3CF3(3)Cl(4) ~_~ m.pOl76-l78o
239 H C6HS H -C~H4CF3(3) m.p.l63(decomp.)
240 H C5H4C1(4~ H-C6H4CF3(3) m-p. 180~decomp.)
241 . H C6H3Cl2(3.4) ~1-C6H4cF3(3) m-p- 161(decomp.)
242 H C6~3~F3(3)C1(4) H C~H4CF3(3) m.p. 169(decomp~)
- - ~ - - .
.;
. : , ` '' ' -`' '':
- 27 -
.
Comp. R5 R6 Rg~10 Physical
. constants
243 H C6H5 ~-C6H3C12(2,4)m,p.179(decomp.)
244 H C6H4C1(3) H-~6H3C12(2,4)m.p.154(decomp.3
245 6 4 ( ) HC6H3C12(2,4)m.p.172C(decomp.)
246 H C6H4CF3(3) H-C6~3C12(2,4)m.p.165(decomp.)
247 H C6H4CH3(3) H-C6H3C12(2,4)m.p.152(decomp.~
24~ H C6H3C12(3,4) H-C6H3C12(2~4)m.p.176(decomp.)
249 H ~6H3Cl2(2~5) H-C6H3C12(2,4)m.p.185C(decomp.)
250 H C6H3CF3(3)C1(4) H -C6H3Cl~(2,4)m.p.162(decomp.)
251 ~ C6H3CH3(2)C1~4) H -C6H3C12(2,4)m.p.154(decomp.)
252 C6H3C~l3(2)Cl(3) H -C6H3C12(2~4)m.p.140(decomp.)
253 H C6H3C12(2,4) H-C6H3C12(2~4)m.p.177~(decomp~)
254 H C6H9C1(3) H-C~H3(CF~2(3,~m.p.165~decomp.)
255 H C6H4Cl(4) ~-C6H3(CF~2(3,~ m,pl79(decomp.)
256 H C6H~CF3(4) H-~6H3(CF~2 (3,5~.p. 188(decomp.)
257 H C6H4Cl(4) H-C6H3Cl(2)N02(4) m-P-187 (decomp.)
258 H C6H4CF3(4) H-C6~13Cl(23N02(4) m-P~198 (decomp.)
~59 H G6H3C12(3,4) H~C6H3C1(2)N02(4) m-p-l98 (dècomp.)
260 H C6H3C1(2)N02(4) H -C6H3C1(2)N02(4) m.p.l85 (decomp-)
., .
261 -CH3 ~H3~ mOp.104-105
262 ~CH3 CH3 H-~6H3CH3~ C1(3) m-p. 164(decomp.)
263 -CH3 _CH3 H ~C6H4CF3(3) m.p. 115-117~
264 -CH3 3 H -C6H~C12(2,5) m~p. 162-164
265 -CM3 CH3 ~ Br m.p. 71-72
; 266 H C6H3C~(2,5) H ~ CH3 m.p. 120(decomp.)
~ Br
., '.~ .,' ' ' ~ .
` ' ; , , ~ 1: . -
~8 ~ 59 ~ 7~
Comp. R5 R6 Rg 10 Physical
. constants
, _ , . . . _
267 H C6H4Cl(3j H CH2CH=CH2 m.p.154 (decomp.)
268 H C6H3~F3~3)C~ H CH2CH=CH2 m.p.l75(decomp.)
269 H C6H3C1(3)CF3(~ H CH2CH=CH2 m.p.l39(decomp.)
270 H C6H4Clt4) H CH2CH=CH2 m.p.l70(decomp.)
271 H C6H3C12(3,4) H CH2CH=CH2 m.p.l64"(decomp.)
272 H -CH3 H CH2CH=CH2 m.p.lll-113
273 H GH(CH3)2 H C2HS m.p,103-105
274 H C3~7 H C2H5 m~p.78-90
275 4 9 C2 5 m.p.70,5-74
276 H C3H7 H CH3 m.p.67-70
277 H CH(CH3)2 H CH3 m.p.116~ 5
278 ~4H9 H CH3 m.p.107-109
279 H CH2-CH2 Cl H CH3 m~pO105~106
280 H C6H4C1~4) H nC3H5 m.pD177-178
281 H C6H3C12(3,4) H nC3H5 m.p.180(decomp.)
282 H C~H3C1(3)C~13(4) H nC3H5 m.pO166-167
283 H -CH3 H nC3H5 m.p.124-126
284 6 4 ( ) H C6H3C12(3,5) m.p.190(decomp.)
285 H C6H3CF3(3)C1(4) H C6H3C12(3,5) oil
286 H C6H3C1~(3,4) H C6H3C12(3,5) m.p.l73(~ecomp.)
2~7 H C6H3Cl(3)CF3(4) H C6H3C12(3,5) m.pO182(decomp.)
288 H C6H4CF3(4) H C6H3C12(3,5) m.p.169(decomp.)
289 ~ CH3CH2Cl H H m.p.l41-142
290 H -CH3 H CH3 ~ m.p.167-168 ;
,' .' .
' .
'
'; ;
~ ~r.7~r~_~
~ ' ' , ''~ ~ ' "' " ",'.',
~. ~` .' ,:
- 29 -
and also the following carbama~es of the formula
.
.~ , .
9 ~ N C C /
Rlo N0-C NnlR
,~. .
Comp. R6 R9 Rlo Physical
No. constants
:
291 C6H4Cl(3) H CH3 m.p.l77-17g
292 C6H4Cl(3) H ~2H5 m.p.166-167
2g3 C6H4C1(3) H H m.p.203(decomp.)
~94 C6H4C1(3) CH3 3 m.p.125-128
295 C6H4Cl(4) H CH3 m.p.l98-200
296 C6H4Cl(4) H Hi mOp,203(decomp.)
297 C~H4Cl(4) H C2H5 m,p.l80~decomp.)
298 C6H4Cl(4) CH3 ~H3 m.p.l61-162
299 CsH3CH3(4)C1(3) H CH3 m.p.l80(decomp.)
300 C6H3CH3(4)C1(3) GH3 CH3 m.p.144-146
301 C6H3CH3(4)C1(3) H C2H5 mOp.163-163,5
302 C6H3CH3(4)~1~3) H C4H9(n) m.p.l42-145
303 C6H3CH3(4)C1(3) H H m.p.l63-16~
304 C6~3CL2(3,4) H CH3 m~p.195(decomp.)
305 C6H3C12(3.4~ H C2H5 i m.p.l75~5~decomp.)
306 C6H3C12(3,4) H C4Hg m.p~l67,5-170
307 ~6~3G12(3'4) ~ H m.p.l92-193
308 C6H3CF3(3)C1(4) H ~H3 m.p.l98(decomp.)
309 C6H3CF3(3?C1(4~ H C2HS m.p.l85(decomp.)
310 ' C6H3CF3~3)C1(4) H H m.p,183(decomp.)
311 C6H3CF3(3)C1(4) H ~3Hi7(n) m.p.l72(decomp.)
31Z C6H3CF3(3)Cl~) H C~H9~n) m.p.l74-177
.~;
:
. : , , i ~ ,- .
~s~
- 30 -
.
Comp, R6 R9 Rlo Physical
constants
___ _ . _ . . . . . . ...
313 C6H3C1(3)CF3(4) CH3 3 m.p. l56-158
314 C6H3C1(3~ CF3(4) H H m.p. 191(decomp.)
315 C6H3C1(3) CF3(4) H C~3 m.p. 183-185
316 C~j,H3C1(3)CF3~4) H C2HS m.pO 167-169
317 C6H3C1(3~CF3(4) H C4H9(n) m.p. 149-150
318 C6H~CF3(~) H H m~p. 183(decomp.)
319 C6H4CF3(2) H CH3 m.p. 193(decomp.)
320 C6H4CF3(4) H H m.p. 180(decomp.)
321 C6H4CF3(4) ~ ~H3 m.p. 18~ (decomp.)
322 C~,H4CF3(4) ~13 ~H3 m.p. 134-135
323 C6H4Cl(3) H C3H~(n) m.p. 155 157
324 C6H4C1(4) H C3H7(n~ m~p. 170(decomp.)
325 C6 4C (4) ltl C~H9(n) m.p. 170-174
326 C6 3 2(3~5) 11 H m.p. 200(decomp.)
327 C6H3C12(3,5) H ~2~5 m.p. 159(decomp.)
328 C~H3C12(3.5) H CH3 m.p. 194(decomp.)
329 C6H4CF3(3) H CH3 m.p. 190(decomp.
330 C6H~CF3(3~ CH3 3 m.p. 109 110
331 C6H5 lH H mOp. 175(decomp.)
332 C6H5 H CH3 m.p~ 162-163,5
333 C6H3C12(2,3) H H m.p. 156(decomp.)
334 ~H H H m.p. 177~decomp.)
335 ~H2CH3 ~ H m.p. 116-120
336 CH3 H C2H5 m.p. 119,5-124
337 C3H7(n) H H m.p. 113~116
338 C6H3C1(3)CH3(4) H H m.p. 163-164
339 C6H3CH3(4)Cl(3) H CONH2 m.pO 197 (decomp.)
340 C6H3C12(3,4) H CONH~ m.p.205(decomp.)
341 C6H3CF3(3) C1~4) H CONH2 m.p.200(decomp.)
342 C6H4Cl(3) H C02~l2 m.p.206(decomp.)
343 C6H3C1(3) CH3~4) H CONH2 m.p. 197~decomp.)
344 C6~3C12(3~5) ~NH2 m.p. 197(decomp.)
.
.
, . . .
.
. :
~159~37~L
- 31 -
.
Comp. R~ R R Physical
No. constants
,~ :
345 C~H4CF3(3) H CONH~ m.p.208(decomp.)
1 346 C6H5 ~ CONH2 m.p.214-215
.~ 347 C6~3C12(2,3) H CO~H2 m.p.203(decomp.)
348 ~H3 H CONH2 m.p.216(decomp.) ;
and also following carbamates of the formula:
,
H~N-C0-NH-C0-C-CN
N-0-C0-NH-R6
Comp, R6 Physical
; No, constants
;i 349 C4H9(n) m.p. 131(decomp.)
350 C3H7(n) m.p. 133o(decomp~)
35~ C3H7(iso) m.p. 207(decomp.~
352 -CH2-CH2-Cl m.p~ 140-145(decomp.)
353 C3H7(iso) m.p. 2o7o(decomp.)
. , ~
.-.
The following (thio)carbonates are produced according
to Example 3 or by one of the methods given in the
foregoing:
. R 10 -NH -C -C -CN
N-0-C~YR
ll 7
''' ' ' ' ~ .
. .
,
.
.~ ~
. - . ,. . . ... ; ....... : ; ~ . - .
:. . . . : . . . :
, . ~ . .
~, ~ , "
- 32 ~ 5~
Comp. Y~7 ~10 Physical
No. constants
354 OC6H5 H m.p.l49 ~decomp.)
355 OCH3 H m.p.170 (decomp.)
356 oc3H7~iso) H m.p. 171-173
3 m.pO~7_9~,50
358 0C4H9(n) H m.p.l65-167
359 OC3H7(iso) CH3 m.p.109-110
360 0(CH233CH3 CH3- m.p.75-76
361 ~CH3 H m~p.120 1214
362 OCH3 C~3 m.p.73-74
363 C6~5 -~ONH2 m.p.168 (decomp.)
364 OCH3 -CONH2 m.p.171-172
,365 SC2W5 H m.p.l24-125
366 0C4H9(n) -CONH2 m.p.173(decomp.)
367 3 7( ) -CONH2 m.p.l73(decomp~)
~68 SC2H5 ~CONH2 mOp.l790(decomp.)
369 SC2H5 CH3 m~p.76-78~ .
.
.
- .
, ~ :
,
~1 5~7~L
- 33 - -
.
In the manner described in Example 3 or by one of the
methods described in the foregoing, there can be produced
following carbonat~s of the formula:
R
2 \ ~ C-CN
N-0-C0-G
,~ ' , , .
Comp. Rl R2 ~ Physical
No. constants
.. . .. _ . . . . ., . _
370 H H -0-C6H5 ~.p. 105-108
371 H H ~0-isoC3H7 m.p. 108-110
372 H H -0-C~12CH20CH3 oil
373 H ~ -O~H3 m.p. 108-110
374 H H 0 CH~ CC13 solid
375 H H -o~C6H4N0~4) solid
376 ~ H -S-nC4H~ -
377 ~ H -0-tert.C4H9 m.p~ ~5-86
378 H H -S-C2H5 m.p. 59~62
379 3-C1 4-Cl -S-C2H5 . oil
380 H 4-Cl -S-C2H5 oiL
381 2-C1 4-Cl -S-C2H5 -'oil
382 H 4-C~ -S-C2H5 oil
383 H H -o-c6H4cl(4)
384 ~ 4-Cl -0-sec.C4H9
385 H 3-CF3 -0-CH3
386 ' H 3 CF3 -0-C6H5
387 H 3~CF3 -S-C2H5
388 H 3~CF3 -S-CH3
389 H - 4-Br S C2H5
,
.
,. - . .
,
. i . . : :.
~ _ 34 ~ Y~
Comp. Xl R2 G Physical
No. constants
390 H 4-~30 -o-C6H4-OCH3(4~ . oil
391 H 4-CH30 0 C6H4Cl(4~ viscous
; 392 H 4~C2~50-0-isoC3H7 oil
'~' .
and also the ~following carbonates of ~he formula:
'
.' ~1 .
R2 ~-- C-X
- ~ N-0-C0-G
Comp. Rl ~2 ~ G Physical
.~ No. constants
. .
393 H 4_(?~H3) 2N H ~C2~5 oil
394 H 4-~H30 H -S-~2H5 oil
395 H 4-Cl -C~?~CH3 ~OC~3 ~il
':
and the following compounds:
. :
No. 396 H2N C0-NH-C0-C-CN . m.p. lg40tdecomp.)
~ .
N0-C0-N-0-CH
: CH3
No.397 NH2~CO-C-CN m.p~144-146
n (decomp.)
N0-C0-N-0-CH
CH3
.
.
.
- ..
,
.; ~ ~ ..
~ .
.,
~ 35 ~ ~5~7~
No. 398 Hsc6-c(cl~No-co-NHcH3 oil
No. 399 H5C20-CO-C(CN)=NO-CO-SC2H5 oil
No, 400 H5C2 Co-c(cH3)=No-co-NHcH3 m.p.83-85
No. 401 ~ NH-CO-CH=NO-CONHCH3 m.p. 126(decomp.)
CF3
.: .
. ~ .
~ No. 402 C ~ NH-CO-~H=NO-CONHCH3 m.p. 145o(decomp.~
I .
CF~
No. 4Q3 H3C ~ NH-CO-CH-NO CONHCH3 m.p.l70(decomp.).
, .
.
~.
'"
.
.
,
- . ~. :,
., : . :
~. . . ~ , ,i ~
- 36 ~ 7~ ~
As already mentioned, various methods and techniques
are suitable ~or application of ~he compounds of the
formula I for the protection of cultivated plants against
agricultural chemicals:
a) Dressing of the seed with an active substance formu-
lated as a wettable powder by shaking in a vessel until
there exists a uniform distribution over the surface of
the seeds (dry dressing). The amount of active substance
of the formula I used for this purpose is about 10 to
500 g ~40 g to 2 kg of wettable powder) per 100 kg of seed.
b) Dressing of the seed with an emulsion concentrate of
the active substance of the formula I using method a~
~wet dressing).
c) Dressing by immersion of the seed in a liquor con-
taining 50-3200 ppm of active substance of the formula I
for 1-72 hours andg optionally, subsequent drying of the
seed (immersion dressing).
The dressing of the seed or the treatment of the
germinated seedlings are naturally the preferred methods
of application because the treatment with the active
substance is directed completely at the target crop.
There is used as a rule 10 g to 500 g, preferably 50 to
2so g~ of active substance per 100 kg of seed, it being
possible, depending on the method used, which method
enables also the addition of other active substances or
micronutrients to be made, to deviate either upwards or
downwards from the given limiting concentrations (repeat
dressings).
2) Application as a_tank mixture
A liquid preparation of a mixture of antidote and
~ 5
- 37 ~
herbicide (reciprocal quantitative ratio between 1:20
and 5:1 is used, the applied amount of herbicide being
0.1 to 6 kg per hectare. A tank mixture of this type is
preferably applied before or immediately after sowing 7 or
is worked into the unsown soil to a depth of 5 - 10 cm.
3) Application into the seed _urrow
The antidote is introduced, as an emulsion concentrate,
wettable powder or granulate, into the open sown seed furrow
and, after covering of the seed furrow in the normal manner,
the herbicide is applied using the pre-emergence process.
Essentially, the antidote can therefore be applied
before, together with, or after the herbicide, and its
application to the seeds or to the field can be effected
either before or after sowing, or in certain cases also
after germination of the seed.
4) Controlled release of a_~ive substance
The active substance in solution is absorbed onto
mineral granulate carriers or onto polymerised granules
(urea/formaldehyde), and the material is allowed to dry.
It is possible if desired to apply a coating (coated
granules), which enables the active substance to be re-
leased in controlled amounts over a specific period of time.
The term r'seed" within the meaning of the foregoing
is not limited to kernels (o~ cereals, etc.j but encompasses
~11 propagative organs of cultivated plants. By the term
"propagative organs" are meant all generative plant
parts which can be used for the propagation o~ the
cultivated plants. These parts include kernels, roots,
fruits, tubers, rhizomes and stalks, and also emerged plants
and seedlings which are intended for transplanting.
It,is naturally possible to employ also all other
known methods o~ applyin~ active substances. Examples
in this connection are given later in the text.
' .
,~ :
.
-
- 3$ -
The compounds of the formula I can be used on their
own or together with suitable carriers and/or other
additives. Suitable carriers and additives can be solid
or liquid and they correspond to the substances common
in formulation practice, such as natural or regenerated
mineral substances, solvents, dispersi.ng agents, wetting
agents, adhesives, thickeners, binders and/or
fertilisers.
The content of active substance in commercial compo-
sitions is between Q.l and 90 %.
The compounds of the formula I can be in the following
forms for application (the weight-percentag~ figures in
brackets signify advantageous amounts of active substance):
_ _ : dusts and scat~ering agents (up to
10%), and granulates Icoated granules,
impregnated granul~s and homogeneous
granules] tl to 80%),
iquid preearations:
a~ water-dispersible concentrates of active substance:
wetta`ble powders and pastes ~25 to
90% in the commercial packing, 0.01
to 15% in ready-for-use solutions);
emulsion concentrates and solution
concentrates (10 to 50%; 0.01 to 15%
in ready-for-use solutions);
b) solutions (0.1 to 20%) and aerosols.
The active substances of the formula I of the present
invention can be ormulated for example as follows.
,, , _ ___,__, _ __. _,,, __, .. __ _ ._ .. , ,., ._ ~ ., .. _.. ...... . _ _ __ . _.. _ .. _ _._ ._._ _ _.______ __.. ____.. _- .. ~- .. - . - - - _--
. ~.- .r~
"' ~', ,
,., !' .
, ~, , ' " ~
. ' ' ' ' . .
~ 7
- 39 -
Dust: The following substances are used to produce a) a
5% dust and b) a 2% dust:
a) 5 parts of active substance, and
parts of talcum,
b) 2 parts of active subs~ance,
- 1 part of highly dispersed silicic acid, and
97 parts of talcum.
. . .
~ The active substances are mixed and ground with the
:~ carriers, and in this form they can be applied by dusting.
Granulate: The following substances are used to produce a
5% granulate:
parts of active substance 9
0.25 part of epichlorohydrin,
0.25 part of cetyl polyglycol ether,
3.50 parts of polyethylene glycol, and
91 parts of kaolin (particle size 0.3 0.8 mm).
;; The active substance is mixed with epi.chlorohydrin; and dissolved in 6 parts of acetone~ and the polyethylene
glycol and cetyl polyglycol ether are then added. The
- solution thus obtained is sprayed onto kaolin, and the
~ acetone is subsequently evaporated off in vacuo.
; Wettable powder: The following constituents are used to produce a) a 70% wettable powder, b) a 40% wettable
powder, c) and d) a 25% wettable powder3 and e) a 10%
wettable powder: -
~) 70 parts of active substance,
5 parts of sodium dibutylnaphthylsulfonate,
3 parts of naphthalenesulfonic acid/phenolsulfonic
acid/formaldehyde condensate 3:2:1,
; 10 parts of kaolln, and
12 parts o Champagne chalk;
,, ' . . . .
... ,.. ... , . . . . ... .... .. .. . . . : .. . . . ,
.
.. . ., -
:
. . .. . . ~ . .
- . .
: ~ : . .. . . .
- : . , : :: ,. ~
'` ' t ~'' , "
~ ~ S~ ~7
- 40 -
b) 40 parts of active substance,
5 parts of sodium lignin sulfonate,
1 part of sodium dibutylnaphthalenesulfonate,
54 parts of silicic acid;
c) 25 parts of a~tive substance,
4.5 parts of calcium lignin sulfonate,
1,9 parts of Champagne chalk/hydroxyethyl
: cellulose mlxture (1:1),
1.5 parts of sodium dibutylnaphthalenesulfonate,
19l5 parts of silicic acid,
19.5 parts of Champagne chalk, and
28.1 parts of kaolin;
d) 25 parts of active substance,
2~5 parts of isooctylphenoxy-polyoxyethylene-
ethanol,
1.7 parts of Champagne chalk/hydroxyethyl-
cellulose mixture (1:1),
8.3 parts of sodium aluminium silicate,
16,5 parts of kieselgur, and
46 parts of kaolin, and
. e) 10 parts of active substance,
3 parts of a mixture of the sodium salts of
saturated fatty alcohol sulfates,
: 5 parts of naphthalenesulfonic acid/formaldehyde~
condensate, and
82 parts of kaolin.
The active substances are int-imately m;xed in sui~able
mixers with the additives, and the mixture is then ground
in the appropriate mills and rollers. There are obtained
wettable powders which have excellent wetting and suspension
properties, and which can be diluted with water to give
suspensions of the desired concentration.
:. .
.,, .. .... . . , . .. . . .. . .. .. ..... .... . . ... . . . ~ . . ~ .. . ..... ... . . . . .
~ , -, - , ~ ' ' ~.
.. . . .... ..
., , ~ ., . . :
Emulsifiable concentrate: The following subs-tances are
used to produce a 25% emulsifiable concentrate:
parts of active substance,
2.5 parts of epoxidised vegetable oil,
parts of an alkylarylsulfonate/fatty alcohol
` polyglycol ether mixture,
5 parts of dimethylformamide, and
57.5 par~s of xylene.
Emulsions of the desired concentration can be pre-
pared from these concentrates by dilution with water.
Post~emer~ence antidote test in nutrient solution
General procedure
'~ '
Plastic flower pots (upper diameter 6 cm), which
have a pierced bottom, are filled with Zonolite and
the cultivated seeds are sown therein. The pot is placed
into a second transparent plastic flower pot (upper
diameter 7 cm) in which there is 50 ml of water, which
rises by capillary attraction and wets ~he seeds. From
the 5th day the continuous loss of water is compensated
with Hewitt nutrient solution. From the 15th day, when
the cultivated plants are in the 1 1/2- to 2-leaf stage,
there is added to the nutrient solution, made up again
to 50 ml,
10 ppm of the antidote to be tested ~ the
amount of herbicide given below. -
From the 16th da~, the loss of liquid is again made up
with pure Hewitt nutrient solution. During the entire
` duration o~ the test, the temperature is ~0-23C with a
relative humidity of 60-70%. Three weeks after addikion
of the herbicide and antidote, an evaluation is made on
the basis of a linea scale from 1 to 9, with 1 signifying
total plant destruction, and 9 an unimpaired condition of
health of the cultivated plants.
.. . .... .
., , ,. .:
- ,-. ~ : : : ~ . . ..
~: , . . - . : . ;
~L~5
- ~2 -
Test variants
.
1) 15 ppm of a-[4-(3,5-dichloropyridyl-2 oxy)-phenoxy]-
propionic acid propargyl thiol ester in wheat of the
"Zenith" variety;
2~ 4 ppm of 4~ethylamino-6-tert-butylamino-2-chloro-
s-triazine in wheat of the "Zenith" variety;
3) 2 ppm of ~-[4-(p-~rifluoromethylphenoxy) phenoxy]-
propionic acid n-butoxyethyl ester in maize of the
"Orla" variety;
4) 8 ppm of a-l4-(p-trifluoromethylphenoxy)-phenogy]-
propionic acid-n-butoxyethyl ester in sor~hum-millet
of the "Funk G-522" variety;
S) 4 ppm of Prometryne = 2,4-bis-(isopropylamino)-6-
methylthio-s-triazine in sorghum-millet of the "Funk
G-522" variety; and
6) 8 ppm of a-[4-(3,5-dichloropyridyl-2-oxy)-phenoxy]-
propionic acid methyl ester in wheat of the "Zenith"
variety.
Compounds of the formula I have a good antidote
action in these tests. The following results are given
as examples:
Test variant Compound No. Rating of the
herbicidal effect
(without/with
antidote)
1 91 6t8
6 54 3/7
6 372 2/S
' '' ' ' .
. '
.~ ' .
.. ,.. __ ~_.. _ .. _..... . . . _ _ _ . _ .... .. _ .. _. _.. _.. _.. , ... .... _~ . _ _. .. _ .. ~, . _.. _ _.. _,__._., _ . _. . __ _.__, __ ~_ _5 ..
_ .~ ,.,__ ,_,,, .. __, _, .,_ _ _ ,,,, . _, ~_ _ ,_ ~, . "
' ~ ' ' , , ' ' , '
~159 0'7
- 43 -
Pre-emergence antidote test in_nutrient solution
A Hewitt nutrient solution is prepared, which contains
the amount of herbicide given below and 10 ppm o the
antidote to be tested.
There is used cultivated seed which could be expected
to suffer damage from the employed herbicide at the
given test concentration, and the seed is sown in granu-
lated Zonolite (= expanded vermiculite~ which is contained
in a plastic flower pot having a pierced bot~om (upper
diameter 6 cm). This pot is placed into a second tran-
parent plastic flower pot (upper diameter 7 cm), in which
there is about 50 ml of the nutrient solution that has
been prepared with herbicide and antidote; this solution
then rises by capillary attraction in the filler material
of the smaller pot and wets the seed and germinating plants.
The loss of liquid is made up daily with pure Hewitt
nutrient solution to SO ml Three weeks after commencement
of the test, an evaluation is made on the basis of a
linear scale from 1 to 9, with the rating 1 signifying
total plant destruction, and the rating 9 signifying an
unimpaired condition of health of the plants. The control
solution used in a parallel test contains no antidote
addition.
There are used the following:
13 4 ppm of Prometryne = 2,4-bis-(isopropylamino)--6-
methylthio-s-triazine in ~D~Y:I~LLI:E of the l'Funk
G-522" variety;
2) 4 ppm of 4-ethylamino-6-tert-butylamino-2-chloro-s-
triazine in wheat of the "Farnese" variety;
3) 4 ppm o a-14-~p-trifluoromethylphenoxy)-phenoxy~-
propionic acid-n-butoxyethyl ester in barley of the
'~azurka" variety;
~ . .. , . ..................... . . ; ~ .
. . ~ . , ,
~5~
- 44 -
4) 5 ppm o Metolachlor = N~ methyl-2-methoxy~ethyl)-
N chloroacetyl-2-ethyl-6-methylaniline in
of the "Funk G-522" variety; and
5) 1 ppm of 2-methoxy-4,6-bis-(~-methoxy-propylamino)-s-
triazine in sugar_beet of the '~leinwanzleben" variety~.
Compounds of the formula I exhibited in these tests
a good antidote action. The following results may be
given as examples:
Test variant Compound No. Rating of the herbi-
cida'l effect (without/
with antidote~
~ 73 2/5
-; 4 93 2/5
- 4 396 ~/5
4 4 3l7
4 19 2/6 (with 1 ppm
antidote
, concentration)
, 5 19 2/5
36 1/5
3 96 2/5
' 5 112 1/7 (with 1 ppm
antidote
~` `concentration)
4 52 2/5
2/5
_.
...
.,
. .
.~ . '. . '
.
,. . .
., ,
~, .
;~ . :
, . ~ . ,, . ~ . . , . -
, - . .
. , " , . ,. , " ,. . . . ..
~ 7
- 45 -
Antidote test with seed soakin~
Rice seeds of the IR 8 variety are saturated during
48 hours with solutîons of the test substances of lO or
lOO ppm concentration. The seeds are subsequently allowed
to dry for about 2 hours, until they no longer stick
together. Rectangular plastic pots (8 x 8 cm, lO cm in
height) are filled up to within 2 cm of the edge with
sandy loam. In each pot is sowed 4 g of seed, and the
seed is only very slightly covered (about the diameter
of a seed)O The soil is maintained in a moist (not
boggy condition). There is then applied either the
herbicide N~ methyl-2-methoxyethyl)-N-chloroacetyl-2-
ethyl-6-methylaniline or N-propoxyethyl-N-chloroacetyl-
2,6-diethylaniline in dilute solution and in an amount
which converted corresponds to 1.5 kg of active substance
per hectare. An evaluation is made 18 days aEter planting
on the basis of a linear scale from l to 9, according to
which the rating l signifies total plant destruction,
and the rating 9 an unimpaired condition of health of the
plants.
Compounds of the formula I exhibit in this ~est a
good antidote action. The following results may be given
as examples:
.
Compound No. Rating of the herbicidal
- : effect (withou~/with
antidote
,
lOO ppm 396 2/5
397 2/5
10 ppm 90 l/4
138 2/5
.
'~ .
;~
:. :. . , ~ , .
.
.
9~7~L
- 46 -
Pre-emer~,ence antidote test (basic te~t)
General procedure:
Small flower pots (upper diameter 6 cm) are filled
with garden soil, into which the cultivated plants are
sown, covered over and lightly pressed down. The sub-
stance to be tested as antidote is ~hen sprayed on as-a
diluted solution (obtained from a wettable powder) in
an amount corresponding to 4 kg of active substance per
hectare. The herbi~ide is afterwards sprayed on in a
similar manner. After a standing time of 18 days at about
20-23C with 60-70% relative humidity, an evaluation is
made on the basis of alinear scale from 1 to 9, according
to which the rating 1 signifies total plant destruction,
and the rating 9 an unimpaired condition of health of the
cultivated plants. Plants without antidote protection
are used in control tests.
The following are used:
1) 1~5 kg of active substance per hectare of a-[4 (p-
trifluoromethylphenoxy)-phenoxy]-propionic acid-n-butoxy-
ethyl ester in maize of the "Orla 264" variety;
2) 1.5 kg of active substance per hectare of Metolachlor
N-(l-methyl-2-methoxyethyl)-N-chloroacetyl-2-ethyl-6-
methylaniline in sor~hum-millet of the Funk G-522" variety;
3) 2.0 kg of active substance per hectare of Prometryne
= 2,4-bis-(isopropylamino)-6-methylthio-s-tria~ine in
soYa bean;
4) 2.0 kg of active substance per hectare of 4-ethylamino-
6-tert-butylamino-2-chloro-s-triazine in wheat of the
"Farnese" variety;
5) 4.0 kg of active substance per hectare of Prometryne
c 2,4-bis-~isopropylamino)-6-methylthio-s-triazine in
sorghum-millet of the "Funk G-522" variety;
.~ .
~ . . . : . , . - . . . - .
7~
. - 47 -
6) 2.0 kg of active substance per hectare of ~- [4- (p-
trifluoromethylphenoxy)-phenoxy]-propionic acid-n-
butoxyethyl ester in barley of the "Mazurka" variety; and
7) 1.0 kg of active substance per h~ctare of N-methoxy-
ethyl-N-chloroacetyl-2,6-dimethylaniline in maize of
the "Anjou 196" variety.
Compounds of the formula I exhibit in these tests
a good antidote action. The following results are given
:~ as examples.
Test variant Comp. No. Rating of the herbicidal
effect ~without/with
antidote
6 138 4/7
398
4 31 ~/4
7 Sl 2/S
3 378 2/5
:
.; . .
-
. ; ; : .
~, : .
. ~
, : ,.: .
~5~7~L
- 48
.
Antidote action on transplanted rice with separate
application (antidote pre-emergence -~ herbicide post-
emergence)
Plastic pots (8 x 8 cm9 10 cm in heigh~) are filled
to within 2 cm of the edge with soil in the boggy-wet
condition. The substance to be tested as antidote is
sprayed in dilute solution, onto the surface, in an
amount corresponding to 4 kg of active substance per
hectare. Rice plants of the "IR-87' variety in the l 1/2-
to 2-leaf stage are transplanted into the pots prepared
in this manner. The water level is raised to about 1.5 cm
on the next day. Four days after transplanting~ there
is added to the water 2-ethylamino-4-(1,2-dimethyl-n-
propylamino)-6-methylthio-s-triazine in granular form
in an amount which, when converted, corresponds to
0.75 kg of active substance per hectare. The temperature
during the duration of the test is 26-28C, and the
relative humidity is 60-80%. Twenty days after treatment
with the herbicide, an evaluation is made based on a linear
scale from 1 to 9, the rating 1 signifying total plant
destruction, and the rating 9 unimpaired condition of
health of the cultivated plants. Plants without antidote
protection are used in control tests.
Compounds of the formula I exhibit in this test a
good antidote action. The results below are given as examplPs.
Comp. No. Rating of the herbicidal effect
(without/with antidote)
396 3/6
42 S/7
,'
: .
:,' ' -, ' -' ~
,
