CA1159071A

CA1159071A - Oxime carbamates and oxime carbonates for the protection of cultivated crops

Info

Publication number: CA1159071A
Application number: CA000310206A
Authority: CA
Inventors: Henry Martin
Original assignee: Ciba Geigy Investments Ltd
Current assignee: Novartis AG
Priority date: 1978-08-31
Filing date: 1978-08-29
Publication date: 1983-12-20
Also published as: GB2028797A; NL7808962A; FR2434802B1; AU3938078A; AT365410B; ATA601378A; BE870066A; AU530210B2; SE446926B; JPS5535002A; LU80165A1; DE2837204A1; GB2028797B; FR2434802A1; SE7808906L

Abstract

ABSTRACT OF THE DISCLOSURE

Oxime carbamates and oxime carbonates of the formula I given herein are suitable as antidotes for the pro-tection of cultivated plants against harmful agricultural chemicals, in particular against herbicides which are insufficiently compatible with the cultivated plants.
These compounds of the formula I can be used either on their own or together with the agricultural chemicals.
One of the possibilities offered is the dressing or immersion treatment of s ed or of seedlings, of the crop to be protected, with solutions or dispersions of compounds of the formula I.

Description

~5~

The present invention rela-tes to oxime carbamates and oxime carbonates of the general formula I

Ar - C - CN
: 11 ~I), 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

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~

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 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

Example l , ,~ Production of ~ C-CN [Comp. 1}

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 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 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 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 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 - -and also following carbamates Qf the formula:

, I ~
- ~ ~ R5 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 82 -COO~H5 3-CF3 H H ~13 84 ~13 4-CH30 H H ~H3 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 .~ , "
~. . . .

:. ,-.
.
,:~
. .
.

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 100 -COOt.~H9 H H H ~H3 101 ~COOCH3 H 4-Br H ~H3 103 -COOCH3 H 4-Cl H -C6HS

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 . .
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.182-138 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 -0 j ~5 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 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.) 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 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~) - - ~ - - .
.;

. : , ` '' ' -`' '':

.
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~_~

~ ' ' , ''~ ~ ' "' " ",'.', ~. ~` .' ,:

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~

.
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

.
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

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

.
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

,~ ' , , .

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 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.) ~ .

: CH3 No.397 NH2~CO-C-CN m.p~144-146 n (decomp.) .
.
.

- ..

, .; ~ ~ ..
~ .
., ~ 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.) .: .
. ~ .
~ 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 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 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 ' '' ' ' .

. ' .~ ' .

.. ,.. __ ~_.. _ .. _..... . . . _ _ _ . _ .... .. _ .. _. _.. _.. _.. , ... .... _~ . _ _. .. _ .. ~, . _.. _ _.. _,__._., _ . _. . __ _.__, __ ~_ _5 ..
_ .~ ,.,__ ,_,,, .. __, _, .,_ _ _ ,,,, . _, ~_ _ ,_ ~, . "

' ~ ' ' , , ' ' , ' ~159 0'7 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~

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 ' 5 112 1/7 (with 1 ppm antidote ~` `concentration) _.
...

., . .
.~ . '. . ' .
,. . .
., , ~, .
;~ . :
, . ~ . ,, . ~ . . , . -, - . .

. , " , . ,. , " ,. . . . ..

~ 7 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 10 ppm 90 l/4 .

'~ .
;~

:. :. . , ~ , .

.
.

9~7~L

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 4 31 ~/4 7 Sl 2/S

:
.; . .

-. ; ; : .

~, : .
. ~
, : ,.: .

~5~7~L

.

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) ,' : .
:,' ' -, ' -' ~

,

Claims

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A process for protecting cultivated plants from being damaged by harmful agricultural chemicals, which process comprises applying to said plants or parts thereof, or to the locus of their growth, a compound of the formula ( I ) in which Ar is a phenyl group of the formula 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, NO2, lower alkyl, CF3, 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, CF3, methoxy or ethoxy,or b) radical -YR6, in which Y is oxygen or sulfur and R6 is as de-fined above.

2. A process according to Claim 1 comprising use of compounds fo the formula I in which Ar is a thiophene ring unsubstituted or substituted by halogen or lower alkyl, and wherein the substituents Y, R5 and R6 have the meanings given in Claim 1.

3. A process according to claim 1 comprising the use of a compound of formula I in which Ar is phenyl, R2 represents 3-chloro, R3 represents 4-chloro, and R is a tertiary-butylamino group.

4. A process according to claim 1 comprising the use of a compound of formula I in which Ar is phenyl, R2 represents hydrogen, R3 represents 3-tri-fluoromethyl and R is methylamino.

5. A process according to claim 1 wherein Ar is an .alpha.-naphthyl group and R is a diethylamino group.

6. A process according to claim 1 wherein Ar is a 5-chloro-2-thienyl group and R is methylamino.

7. A compound of the formula (I') in which a) Ar is phenyl and R is 2,2,2-trichloroethoxy or 3-trifluoromethyl-phenylamino, or b) Ar is 4-chlorophenyl and R is 4-chlorophenylamino, or c) Ar is 2,4-dichlorophenyl and R is 3,5-di-(trifluormethyl)-phenylamino, or d) Ar is 3,4-dichlorophenyl and R is 4-chlorophenylamino or tert.-butyl-amino, or e) Ar is 4-tert.-butylphenyl and R is 3,4-dichlorophenylamino, or f) Ar is 3-trifluoromethylphenyl and R is methylamino, or g) Ar is .alpha.-naphthyl and R is diethylamino, or h) Ar is 2-thienyl and R is 3,4-dichlorophenylamino, or i) Ar is 5-chloro-2-thienyl and R is methylamino.

8. A compound of the formula I' as defined in claim 7 which compound is N-[(2,2,2-trichloroethoxy)-carbonyloxy]-imino-benzacetonitrile.

9. A compound of the formula I' as defined in claim 7 which compound is N-[(3-trifluorornethylphenyl)-aminocarbonyloxy]-imino-benzacetonitrile.

10. A compound of the formula I' as defined in claim 7 which compound is 4-chloro-N-(4-chlorophenylaminocarbonyloxy)-imino-benzacetonitrile.

11. A compound of the formula I' as defined in claim 7 which compound is 2,4-dichloro-N-[3,5-di-(trifluoromethyl)-phenylaminocarbonyloxy]-imino-benzacetonitrile.

12. A compound of the formula I' as defined in claim 7 which compound is 3,4-dichloro-N-(4-chlorophenylaminocarbonyloxy)-imino-benzacetonitrile.

13. A compound of the formula I' as defined in claim 7 which compound is 3,4-dichloro-N-(tert.-butylaminocarbonyloxy)-imino-benzacetonitrile.

14. A compound of the formula I' as defined in claim 7 which compound is 4-tert.-butyl-N-(3,4-dichlorophenylaminocarbonyloxy)-imino-benzacetonitrile.

15. A compound of the formula I' as defined in claim 7 which compound is 3-trifluoromethyl-N-(methylaminocarbonyloxy)-imino-benzacetonitrile.

16. A compound of the formula I' as defined in claim 7 which compound is N-(diethylaminocarbonyloxy)-imino-2-naphthalene-acetonitrile.

17. A compound of the formula I' as defined in claim 7 which compound is N-(3,4-dlchlorophenylaminocarbonyloxy)-imino-2-thiophene-acetonitrile.

18. A compound of the formula I' as defined in claim 7 which compound is 5-chloro-N-(methylaminocarbonyloxy)-imino-2-thiophene-acetonitrile.