Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
3'~ 7
.
O.Z. 0050/033621
N~SULFENYLATED DIURETHANES
The present application relates to novel diurethanes, a
process for their manufacture, herbicides containing these com-
pounds as active ingredients, and a process for controlling un-
wanted plant growth with these compounds.
It has been disclosed (German Printed Application
DE-AS 1,567,151) that methyl N-(3~(N'-3'-methylphenylcarbamoyloxy)-
-phenyl)-carbamate may be used as a postemergence herbicide for
combating broadleaved weeds in sugarbeets. Although the compound
is generally well tolerated by this crop, selectivity difficulties
may occur if treatment is effected during emergence or development
of the cotyledons.
Al~ylation of the acidic NH groups of this active ingredient
gives carbamates having relatively poor herbicidal properties
(German Laid-Open Application DE-OS 1,567,163). For instance,
methylation of both nitrogens results in a considerable decrease
in photosynthesis inhibition activity (Z. Naturforsch., 23b~
342-348, 1968).
~, ~ 35~D ~
We have now found that new N sulfenylated diurethanes
of the formula
X ~ / SCFC12 I,
y~= / \COO~
SCFC12
COOR
where R denotes unsubstituted or halogen- or alkoxy-substituted
alkyl, alkenyl or alkynyl, each of up to 5 carbon atoms, and
X and Y are identlcal or different and each denotes hydrogen,
halogen, alkyl, haloal]cyl, alkoxy or alkylthio, each of up to
4 carbon atoms, nitro or cyano, have a good herbicidal action
and are excellently tolerated by crop plants.
R in formula I denotes linear or branched alkyl,
alkenyl or alkynyl, each of up to 5 carbon atoms, e.g., methyl,
ethyl, isomeric propyl, butyl and pentyl, allyl, l-methylpropen-
2-yl~ propargyl, and 1-methylpropen-2-yl.
These radicals may be substituted by halogen, e.g.~
chlorine, or by alkoxy of up to 2 carbon atoms. Examples are
2-chloroethyl, 2-methoxyethyl, 2-chloroallyl, 4-chlorobutyn-2-
yl, and 2-ethoxy-n-propyl.
X and Y in formula I may be identical or different
and denote hydrogen; halogen, e.g., fluorine, chlorine, bromine
and iodine; linear or branched alkyl of up to 4 carbon atoms,
e.g., methyl, ethyl, isopropyl and tert-butyli linear or
branched haloalkyl of up to 4 carbon atoms, e.g., trifluoromethyl
and l-chloroisopropyl; linear or branched alkoxy of up to 4
carbon atoms, e.g., methoxy, ethoxy and tert~b~toxy; linear
or branched alkylthio of up to 4 carbon atoms, e.g., methylthio
and ethylthio; and nitro or cyano.
~139 ~ 7 7
Preferred diurethanes of the formula I are those in
which R is methyl or ethyl, X is hydrogen, chlorine, fluorine,
methyl or ethyl, and Y is hydrogen.
The N-sulfenylated diurethanes of the formula I may
be obtained by reaction of diurethanes of the formula
~NHCOO--~ ` II,
NH-COOR
where R, X and Y have the meanings given for formula I, with
dichlorofluorosulfenyl chloride in the presence of an acid
binder and in a solvent or diluent.
The reaction may be illustrated by the following
equation:
2 CL ~ C12 ~ N-COO
Y .~ ~ y ~ 12
~ICOOR
COOR
Suitable organic binders are organic bases, such as
tertiary amines, e.g., trialkylamines such as triethylamine,
dialkylcyclohexylamines, quinoline or pyridine, and inorganic
bases~ such as hydroxides, bicarbonates or carbonates of alkali
metals and alkaline earth metals, e.g., potassium carbonate,
sodium bicarbonate, calcium carbonate and potassium hydroxide.
The acid binder i5 employed in at least molar amounts, based
on the compound of the formula II, or on dichlorofluorosulfenyl
chloride.
The reaction is carried out in the presence of a
solvent or diluent. Suitable examples are, in addition to water,
organic solvents r such as optionally chlorinated aliphatic and
~39~t~
aromatic hydrocarbons, ketones, ethers, esters or nitriles,
for example methylene chloride, toluene, chlorobenzene,
cyclohexane, petroleum ether, acetone, tetrahydrofuxan, dioxane,
ethyl acetate~ and acetonitrile, and dimethyl sulEoxide,
sulfolane, hexamethylphosphoric triamide and dimethylformamide.
.
- 3a -
~39 ~ ~
0. Z ~ 0050/033621
The reaction is carried out at from -20 to +110C and at
atmospheric or superatmospheric pressure. Preferably, the di
chlorofluorosulfenyl chloride is used in excess, based on the
diurethane of the formula II.
The diruethanes o~ the ~ormula II used as starting materials
are known and may be manufactured by conventional processes
(German Printed Applications DE-AS 1,568,138, 1,657gl51; 1,567,163;
and 2,638,897). The manufacture of dichlorofluorosulfenyl chloride
is disclosed in J. Gen. Chem~ USSR 1959, p. 3362~
The following example illustrates the manufacture of the
compounds according to the invention.
EXAMPLE 1
143 g of methyl-N-( 3-N ' -phenylcarbamoyloxy)-phenyl-carbamate
and 250 g of dichlorofluorosulfenyl chloride in 750 ml o~ toluene
are placed in a receiver. At room temperature, a mixture of 177 g
o~ triethylamine and 500 ml of toluene is dripped in and the
resultant mixture is stirred for 3 hours. The reaction mixture
is extracted by shaking first with 400 ml of ice water, then
3 times with 250 ml of ice-cold 20% strength h~drochloric acid,
20 and again with water. After drying over sodium sul~ate and con-
centration, 100 ml of diethyl ether and 400 ml o~ petroleum ether
are added to the residue and the mixture is filtered after having
been allowed to stand briefly,
~here is obtained 233 g of a crystalline product of melting
point 88 to 89C.
Analysis
calc.: C 37.0 H 2.2 N 5.1 S 11.6 Cl 25.7 F 6.9
found: C 37.1 H 2.~ N 5.2 S 11.6 Cl 25.7 F 6.o
- 4 -
~35a~7~7
The compound has the :Eollowing structural formula:
jCFC12
\ COO ~
SCFC12
COOC~3
The following compounds for instance may be prepared
analogously:
X SCFCl
~ N /
CF12
N \
COOR
No. R X Y m.p.~bC~
2 C2H5 H H 101-103
3 CH3 3-C1 4-CH3
4 CH-C-CH 3-NO2 H
CH2CH2C1 3-CF3 H
6 CH3 3-CH3 H 72-76
7 CH2CE~2OCH3 3-CH3O H
8 CH3 3-CH3S H
9 CH2CH=CH2 3 C2H5 H
C2H5 3-F 4-F
11 C2H5 3-C1 4-F 74-76
12 CH3 4-F H
13 CH(CH3)C_CH 4-Br H
14 CE~3 3-CN H
CH3 3-Cl H
-- 5 --
3~ ~
No . R X Y m.p . LcJ
16 CH3 3 C?H5 H
17 CH3 3-i-C3H7 H
18 CH3 3-F 4-Cl
19 CH3 3-C1 4-Cl
2 CH 3 3 -CH 3 5 -CH 3
21 CH3 3-C1 4--F
- 5a
V~9~ ,
O.Z. 0050/033621
The active ingredients according to the invention may be
applied for instance in the form of directly sprayable solutions,
powders, suspensions (including high-percentage aqueous, oily or
other suspensions), dispersions, emulsions, oil dispersions,
pastes, dusts, broadcasting agents, or granules by spraying,
atomizing, dusting, broadcasting or watering~ The forms of applic~
ation depend entirely on the purpose for which the agents are being
used; in any case they should ensure as fine a distribution of the
active ingredient as possible.
For the preparation of solutions, emulsions, pastes and
oil dispersions to be sprayed directg mineral oil fractions of
medium to high boillng point, such as kerosene or diesel oil,
further coal-tar oils, and oils of vegetable or animal origin,
aliphatic, cyclic and aromatic hydrocarbons such as benzene,
toluene~ xyleneg paraffin, tetrahydronaphthalene, al~ylated
naphthalenes and their derivatives such as methanol, ethanol,
propanol, butanol, chloroform, carbon tetrachloride, cyclo-
hexanol, cyclohexanone, chlorobenzene, isophorone, etc., and
strongly polar solvents such as dimethylformamide, dimethyl
sulfoxide, N-methylpyrrolidone, water, etc. are suit~ble.
Aqueous formulations may be prepared from emulsion con-
-centrates, pastes~ oil dispersions or wettable powders by
adding water. To prepare emulsions, pastes and oil dispersions
the ingredients as such or dissolved in an oil or solvent ma~J be
homogenized in water by means of wetting or dispersing agents,
adherents or emulsifiers. Concentrates which are suitable for
dilution with water may be prepared from active ingredient,
wetting agent, adherent, emulsifying or dispersing agent and
possibly solvent or oil.
-- 6 --
~ 3L3~
O.Z. 0050/033621
Examples of sur~actants are: alkali metal, alkaline earth
metal and ammonium salts of ligninsulfonic acid, naphthalene-
sulfonic acids 3 phenolsulfonic acids, alkylaryl sulfonates,
alkyl sulfates, and alkyl sulfonates, alkali metal and alkaline
earth metal salts of dibutylnaphthalenesulfonic acid, lauryl
ether sul~ate, fatty alcohol sulfates, alkali metal and alkaline
earth metal salts of fatty acids, salts of sulfated hexadecanols,
neptadecanols, and octadecanols, salts of sulfated fatty alco-
hol glycol ethersg condensation products of sulfonated naphtha-
lene and naphthalene derivatives with formaldehyde, condensation
products of naphthalene or naphthalenesulfonic acids with phenol
and formaldehyde, polyoxyethylene octylphenol ethers, ethoxyl-
ated isooctylphenol, ethoxylated octylphenol and ethoxylated
nonylphenol, alkylphenol polyglycol ethers, tributylphenyl
polyglycol ethersg alkylaryl polyether alcohols, isotridecyl
alcohol, fatty alcohol ethylene oxide condensates, ethoxylated
castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxy-
propylene, lauryl alcohol polyglycol ether acetal, sorbitol
es~ers, lignin, sulfite waste liquors and methyl cellulose.
Powders, dusts and broadcasting agents may be prepared by
mixing or grinding the active ingredients with a solid carrier.
Granules, e.gO, coated, impregnated or homogeneous gra-
nules, may be prepared by bonding the active ingredients to
solid carriers. Examples of solid carriers are mineral earths
such as silicic acid, silica gels, silicates, talc~ kaolin,
Attaclay, limestone, lime, chalk, bole, loess, clay, dolomite,
diatomaceous earth, calcium sulfate, magnesium sulfate, mag-
nesium oxide, ground plastics, fertili~ers such as ammonium
sulfate~ ammonium phosphate, ammonium nitrate3 and ureas, and
3~ vegetable products such as grain flours, bark meal, wood meal,
and nutshell meal, cellulosic powders, etc.
3t~
0.~. 0050/033621
The formulations contain from 0.1 to 95, and preferably
0.5 to 90, % by weight of active ingredient. Application rates
are from 0.1 to 15 kg of active ingredient per hectare.
Examples of formulations are given below.
I. 90 parts by weight of compound 1 is mixed with 10 parts by
weight of N-methyl~ pyrrolidone. A mixture is obtained which is
suitable for application in the form of very fine drops
II. 20 parts by weight of compound 2 is dissolved in a mixture
consisting of 80 parts by weight of xylene, 10 parts by weight
of the adduct of 8 to 10 moles of ethylene oxide with 1 mole of
oleic acid-N-monoethanolamide, 5 parts by weight of the calcium
salt of dodecylbenzenesulfonic acid, and 5 parts by wei.ght; o~
the adduct of 40 moles of ethylene oxide with 1 mole of castor
oil. By pouring the solution into 100,000 parts by weight of
water and uniformly distributing it therein, an aqueous dis-
persion is obtained containing 0.02% by ~eight of the active
ingredient.
III. 20 parts by weight of compound 6 is dissolved in a mix-
ture consisting of 40 parts by weight of cyclohexanone,
30 parts by weight of isobutanol, 20 parts by weigh-t of the
adduct of 7 moles of ethylene oxide with 1 mole of isooctyl-
phenol, and 10 parts by weight of the adduct of 40 moles of
ethylene oxide with 1 mole of castor oil. By pouring the solu-
tion into 100,000 par-ts by weight of water and finely distributing
it therein, an aqueous dispersion is obtained containing 0.02%
by weight of the active ingredient.
IV. 20 parts by weight of compound 2 is dissolved in a mix-
ture consisting of 25 parts by weight of cyclohexanol, 65 par~s
by weight of a mineral oil fraction having a boiling point bet-
ween 210 and 280C, and 10 parts by weight of the adduct of
~3~ ~
O.Z. 0050/033621
40 moles of ethylene oxide with 1 mole of caskor oil. By pouring
the solution into 100,000 parts by weight of water and uniformly
distributing it therein, an aqueous dispersion is obtained
containing 0 02% by weight of the active ingredient.
. 20 parts by weight of compound 6 is well mixed with
3 parts by weight of the sodium salt of diisobutylnaphthalene-
-~sulfonic acid, 17 parts by weight of the sodium salt of a
lignin-sulfonic acid obtained from a sulfite waste liquor,
and 60 parts by weight of powdered silica gel, and triturated
in a hammer mill. B~ uniformly distributing the mixture in
20,000 parts by weight of water, a spray liquor is obtained
containing 0.1% by weight of the active ingredient.
VI. 3 parts by weight of compound 1 is intimately mixed with
97 parts by weight of particulate kaolin. A dust is obtained
containin~ 3~ by weight of the active ingredient.
VII. 30 parts by weight of compound 2 is intimately mixed
with a mixture consisting of 92 parts by weight of powdered
silica gel and 8 parts by weight of paraffin oil which has
been sprayed onto the surface of this silica gel. A formulation
of the active ingredient is obtained having good adherence.
VIII. 40 parts by weight of compound 11 is intimately mixed with
10 parts of the sodium salt of a phenolsulfonic acid-urea-form-
aldehyde condensate, 2 parts of silica gel and 48 parts of
water. Dilution in 100,000 parts by weight of water gives an
aqueous dispersion containing 0.04 wt$ of active ingredient.
IX. 20 parts of compound 2 is intimately mixed with 2 parts
of the calcium salt of dodecylbenzenesulfonic acid, 8 parts of
a fatty alcohol polyglycol ether, 2 parts of the sodium salt of
a phenolsulfonic acid-urea-formaldehyde condensate and 68 parts
of a paraffinic mineral oil. A stable oily dispersion is ob-
tained.
9 -
O.Z. 0050/033621
The influence of various representatives of compounds
according to the invention on the growth of unwanted plants in
comparison with prior art active ingredients is demonstrated by
the following greenhouse experiments and e~periments in the open.
I. Greenhouse experiments
The vessels employed were plastic ~lowerpots having a volume
o~ 300 cm3 and which were filled with a sandy loam containing
about 1.5% humus. For the postemergence treatment, the plants were
: first grown to a height of 3 to 10 cm, depending on growth shape.
The active ingredients were then suspended or emulsified in water
as vehicle, and sprayed onto the leaves of the test plants and
the soil by means of ~inely distributing nozzles. The test plants
were set up in cooler or warmer sections of the greenhouse J depen-
ding on their temperature requirements. The experiments were run
~or ~rom 2 to 4 wee~s. During this period the plants were tended
and their reaction to the individual treatments was assessed.
II. Experiments in the open
These results were obtained ~rom very early postemergence
treatments on small plots. The active ingredients, emulsified or
suspended in water as vehicle 3 were applied with the aid o~ a
motor~driven plot spray mounted on a tractor, as soon as the
cotyledons of the crop plants and weeds became visible.
The scale used for assessment of the greenhouse experiments
and the `experiments in the open was 0 to 100~ 0 denoting no
damage or normal emergence, and 100 denoting nonemergence or
complete destruction of at least the visible plan-t parts.
The plant species used in the experiments are listed in
Table 1. The results obtained are given in Tables 2 and 3; they
show that the compounds according to the invention have, compared
with prior art diurethanes, a good herbicidal action on a number
of broadleaved weeds and are better tolerated by certain crop
plants.
- 10
39 ~ni~
O O Z . ()050/0 3362 1
Table 1 - List of plant names
Botanical name Common name
Arachas hypogaea peanuts (groundnuts)
Beta vulgaris sugarbeets
Chenopodium album lambsquarters (goosefoot)
Euphorbia geniculata South American member of
the spurge family
Galinsoga spp. gallant soldier
Glycine max~ soybeans
Lamium amplexicaule henbit
3
~3~
O. Z . 0050/033~i21
d al
o~ ~ ~
o~
G~rl
~0
Ei
~: 3
C O ~ J O
.~ ~L ~ Cr~ I O
O ~1
~ ~ ~ t
S '
~d V ~ .
~d
a
h
~ X ~ .
blJ ~ ,
a~ ~
. ... ~ ~ ~ I O
~¢~
S ~ .
, .
.~~
.
O h
O I O
S:: S ~ I
h r~ ~ ~U ~ I C~
v ~ ~ ~ 7 ' o
o ¢ ~ '~ =o, C~ =o
D E --12--
~3~
0. Z. 0050/033621
t~ O 8 1 00
~ E~ X O ~1 1 ~ .~
1 1 1
0 u7 ~
00 0 1 00 0
C~ ~ ,1
o ~ ~ .
c~ a
~ .
hO ~, e
~D ~! 1
~; 1 ~ 8 cr~
a~ ,
Ir~3 i ~
O ~ :~ ~I t~J I
'
)
t~
r, 1 15-\
~ O ~ I ~ O
S
O ~ V I O i
D O Q. bO O
P~ ~ O - C~ I ~1 0
S S I I h ~ -O
~ U o~
t/~ 3 C~_O ~ =O
O.Z. C050/033621
In addition to the crops mentioned in Tables 2 and 3,
the compounds according to the in~ention may be used for com-
bating unwanted plants in numerous other crops such as the
following:
Botanical name Common name
Allium cepa onions
Ananas comosus pineapples
Arachis hypogaea peanuts (groundnuts)
10 Asparagus o~ficinalis asparagus
Avena Yativa oats
Beta vulgari~ spp. altissima sugarbeets
Beta vulgaris spp. rapa ~odder beets
Beta vulgaris spp. esculenta table beets, red beets
Brasslca napus var, napus rape
Brassica napus var. napobrassica
Brassica napus var~ rapa turnips
Brassica rapas var. silvestris
Camellia sinensis tea plants
20 Carthamus tinctorius sa~flo~er
Carya illinoinensis pecan trees
Citrus limon lemons
Citrus maxima grapefruits
Citrus reticulata
Citrus sinensis orange trees
Co~ea arabica (Coffea canephora,
Coffea liberica) coffee plants
Cucumis melo melons
Cucumis sativus cucumbers
Cynodon dactylon Bermudagrass in turf and lawns
Daucus carota carrots
14 -
0 . Z . 0050/03362
Botanical name Common name
Elais guineensis oil palms
Fragaria vesca strawberries
Glycine max soybeans
Gossypium hirsutum
(Gossypium arboreum cotton
Gossypium herbaceum
Gossypium vitifolium)
Helianthus annuus sun~lowers
Helianthus tuberosus
10 Hevea brasiliensis rubber plants
Hordeum vulgare barley
Humulus lupulus hops
Ipomoea batata~ sweet potatoes
Juglans regia ~alnut trees
Lactuca sativa lettuce
Lens culinaris lentils
Linum usitatissimum ~lax
Lycopersicon lycopersicum tomatoes
Malus spp. apple trees
20 Manihot esculenta ca~sava
Medicago sativa al~al~a (lucerne)
Mentha piperita peppermint
Musa spp. banana plants
Nicothiana tabacum tobacco
(N. rustica)
Olea europaea olive trees
Oryza sativa rice
Panicum miliaceum
Phaseolus lunatus limab eans
Phaseolus mungo mungbeans
3o
Phaseolus vulgaris ~napbeans, green beansS
dry beans
- 15 -
O.Z. 0050/033621
80tanical name Common name
_ _ _
Pennisetum glaucum
Pe~roselinum crispum parsley
spp. tuberosum
Picea abies Norway spruce
Abies alba ~ir trees
Pinu~ spp. pine trees
Pisum ~ativum English peas
Prunus avium cherry trees
10 Prunus domestica p~um trees
Prunus dulcis almond trees
Prunus p~rsica peach trees
Pyrus communis pear trees
Ribes sylve~tre redcurrants
Ribes uva-crispa
Ricinus co~munis
Saccharum of~icinarum sugar cane
Secale cereale r~e
Sesamum indicum se~ame
20 Solanum tuberosum Irish potatoes
Sorghum bicolor ~s. vulgare) grain sorghum
Sorghum dochna
Spinacia oleracea spinac~
Theobroma cacao cacao plants
Tri~olium pratense red clover
Triticum aestivum ~heat
Vaccinium cor~mbosum blueberries
Vaccinium vitis-idaea cranOerries
Vicia faba ti~ck beans
Vigna sinensis (V. unguiculata) cow peas
Vitis vini~era grapes
Zea mays Ind~an corn, sweet corn, maize
- 16 ~
O.Z. 0050/033621
The new herbicidal active ingredients according to the in-
vention may be mixe~ and applied together with numerous represent-
ati~e~ of other herbicidal or growth-regulating ackive ingredient
groups. Examples of suitable mixture components are diazines, benæo-
thiadiazinones, 2,6-dinitroanilines, N-phenylcarbamates~ thiol-
carbamates, halocarboxylic acid~ triazines, amides, ureas, di
phenyl ekhers, triazinones, uracils, ben~ofuran derivatives, etc.
Such combinations broaden the spectrum o~ actionO A number of
active ingredients whichg when combined with the new compounds,
give mixtures useful for widely varying applications are given
below by way of example:
- 17 -
7 ~ ,
O . Z . 0050/033621
R--N~ F~ 1
R \2
O
~ =
NH2 Cl
(~ ~H2 ~r
~ O~H3 OCH3
N(CH3)2 Cl
~} OCH3. . OC~I3
NH2 Cl
~ N(CH3)2 Cl
C~3
~ NHCH3 Cl
CF3
~ OCH3 Cl
C~3
~} NH2 Br
,--~
~ OCH3 OCH3
C~3
3 - 18
;~Q3~
0. Z . 0050/033621
R R1 R2
~ NHCH3 C l
-
F2CHCF20
R2 ~,N -
R R
H 3 7 H H ( salts )
H i-C3H7 H CH3 ( sal~s )
H i C3H7 H Cl ( salts )
CH2~0CH3 3 7 H H
H 3 7 H F t salts )
CH2-OCH3 3 7 H Cl
CH2-OCH3 3 7 H F
CN i 3 7 H Cl
. - 19 -
~3~
0 . Z . 0050/033621
R2 N0 2 3
Rl ~ ~
R N02
H3CS02 H n-C~;H7 3 7
3 H C2~ C4Hg
H F3 n~( 3H73 7
H F3C H CH?`cH2cln~C3H7
Htert-C4Hg H ~ecwC4~g~e~-C4~Ig
E~ S02NH2 :~ n C3H7 n-C3~7
3 ~ C3H7 CH2~a
H H ~ec-C4Hg
H ~jC H3C H H-CH ( C2H5 )
H F3C ~H2 3 7 3 7
H H ~C H n-C3~I7 n--C3H7
H i-C3H7 H n-C3H7 n-C3H~
. - 20 -
O.Z. 0050/033621
--N C ~ 0 ~ R~
F~ / "
R Rl R2
~. .
H 3 7
C~3 ~I ` C~2
Cl
~ . ~ CH3
CH C- CH
Cl
Cl -~ ; C-C-CH Cl
Cl~ J . i~C3~7
CH3 '
H -CH-C NX-C2H5
O
Cl~ . H CH3
C~
? ~so2_ H CH3
CH3 H tert,-HgC~--CH
tert.-HgC4 3
~CH3
H ~CH
3 - 21 -
0. Z . 0050/033621
R
R - N - C ` O 4
8 ~ 2
NH r c o -- R
O
R R~ R;~
. ~ .
~ ~ C~5
C~3
r~
~ ~ C2X~
~H3 ~
~ H C~H5
C~3
~ CH3 C~13
F~ H CH3
F-~_ H C2H~
~ I C2H5
Cl ,.~
F~ H CX 5
F
H ~3
Cl
- 22 -
~3~
0 . Z . 0050/033621
CH3
~3 NH - C ~ O - ~
CF3 N~C-0C~3
~~ - G - S ~ R2
R/
R. . . Rl . R2
i -C3E~7 i ~C3~7 C~2~CCl-CCl~
~ C3 7 i-C3X7 -CH;2- CCl-CHCl
n- ~3H7 3 7 C2~5
~} 2 5 2 ~
sec-C4Hg ~ec-C4Hg C2H5
~l-G3H7 3 7 n-C3H
c~s C2X~ -CX~,l
-
~ec-~C4Hg sec-C4Hg , -CH2~>
Q C2H5 c2H5
i-C3H7 i-C3E~7 CE~ ~C 3
_ 23 _
O.Z. oo50/03362~
i
i-C3~I7 i~C3H7 CH2~ C2~5
CH3
~~C~S R
X n
H3C CH3
-{}I2 CCl=CHCl
~CH;2~CCl-CC12
CN; C S C;2H5
x
R ~ C C - O -
O
CH 3 C1 C1
Na
C1 C1 C1
Na
C1~CH2~ C1 H C~ 3
~C~ O- H H
H ~alts )
O
, . .
C1~0~0 H CH3 ~C~3
C1
7t~
0 . ~ . 0050/033621
R X ~ Rl
~C-N H CH3 C2H5
[~ =
Cl Cl
2 5 Cl Na
~n ~ ~I CH3 i^C3H7
0~
~, Cl
(~C N- H CH3 CH3
[~ .
F Cl
Cl~0~0- H CH3 -CH2-C~3 ( CH3 ~ 2
Cl . . -
. Cl~0~0- H CH3 Na
20F~C~o~0- H CH3 Na
~1
3 ~ ~ H CH3 CH3
25 -
O . Z 1 0050/033621
.
Rl N~ /R2
R N ~R 3
tert-C4Hg SCH3 H C 2H5
HC2H~ SCH3 H C2
Hi-C3H7 SCH3 H C2~
HCH3 SCH3 H i-C3H7
Hi G H Cl H C~H~;
Hi C3 7 Gl H _
KC2H5 Cl H C 2~5
CH3
H C2H5 Cl ~ -C-C;I
K i C H7 Cl H i C3H7
H i 3 7 OCH3 H i-C3H7
N ~ 3 Cl H
CH3
CX3
H C2H5 Cl H -CH-CH2-OCH3
CH3
H C2H5 Cl H -CH~C-CH
-- 2 6
O. Z . 0050/033621
--N C ~ R 2
R ~ Q
R R1 R2
CH3 C~3 CH(C6H~;)2
<~ ' COOH
lO Cl~
Cl
Cl~ ~ ~ 2 H~
Cl
Cl~S~L H C2~5
, 3
Cl~ H . -C~ CX2-~X2-CH3
C}I3
t--\ 7
~ -CH-C-CH C~2Cl
CH 3 CH 3
~ .
CH-C~I2-OCH3 CH2 Cl
C2H5
C2~5
' , -Cx2-ocH3 CX2Cl
C2H,5
- 27
~:~L3~"~
O.Z. 0050/033621
C~
~C -~H2 C-OC2~5 CH2Cl
2 5
<~ iCX CX2C
~ 3 -CH2 0-CH2CH ( C~ 3 ) 2 CH2
CH3
C~X5
H2-O~n~C~Hg CH2C~
C2H~
~3
-C~I2-0-C2H5 CH2Cl
G2H~
CH
~ CH2-<~ C~2t
CH3
C~
~_ 3 -CH2-CH2-OCH3 ~H2Cl
CH3
2 N~-- CH2Cl
CH3
3 - 28 -
~L~3~'~7~
O, Z . 0050/033621
R Rl R2
C. H 3 - CH~ ~N~ CH2 Ci
CH ~ OCH 3
CH
~X3 -C~2~N l C~2
~ H3 CH2 ~ C~2
CH ~ CH3
3 3 t 3~N~
. CH-N~
Br ~r
CH
C2H5 ~2~5 ~C~I-O~
CH2-CH-CH2 CX2-CH-CH2- C~2Cl
3 -CH2~ CH2
,3
CH3 ~CH~ -N~ CH2 Cl
u
c2~5
- 29 -
~L~3~
O . Z . 0050/033621
CH3 Cl
HC_C~C- H ~Cl
C 3
H3C~ H 3
CS02~
CH3
H3C~ H CH~5
F3CS02}~
. . .
NC--~/~0 - R
'
X Y R
Br ar E ( salts 3
H ~ ~alts )
Br Br ~ C-(CH2) 6-CH3
Br
02N ~-O-N=CH-~-C)EI salts, esters
N02 Br
Br
02N ~-O-N=CH-~-OH ~al-ts, esters
CN Br
30~ 30 -
'Y
O.Z.0050/033621
R 1 ~R2
N ~ C - N
~/ 0 R 3
.
i-H7C3~ ~ CH3 CX3
H3 ~ H CH3 CH3
Cl
H C~3 CH3
tert -~19 C 4 HN- C0
O
[~ />~ H CH3 H
~_ CH3 CH3 H
Cl~ H CH 3 C~3
Cl~ H CH3 3
Cl
~ H ~ H
C~3
~ . H C~3 C~3
F3
- 31 -
O. Z . 0050/033621
CH
Cl~ H CH3-CH-C--CH
Br~ H CH3OCH3
H3 ~ H C~ 5CH3
Cl
CH
H3C~ H -C~ H
Cl~ H CH3OCH3
ClF2C~ . H - C~I3CH3
Cl
~ H CX3CH3
Cl~ H CX3C~3
~~~
U H C~3CH3
Cl~ E~ CH3OCH3
Cl
Br~ H CH3oc~3
Cl
- 32 -
'7~ o . z . 0050J03362~
R Rl R2 R3
Cl~ H CH3 H
Cl
N--N
tert~HgC4 ~S~L CH3 CH3 H
N--~t
F 5C I~SJL CX3 c~3 EI
Cl~ H C2H5 c2
.~;;1 . .
.
F2CHCF2 0
~C~
Cl
Cl
H3C0~ 3 CH3
Cl
~ n NX CH2 - CH(CH3)2
~ 33 ~
~L~3~'~"7~
oOZ. 0050/033621
}~2
R 1 ~O~N02
R R3
-
C1 Cl Cl H
F C1 C1 H
N02 CF3 X H
C1 CF3 HCOOH ~ salts )
C1 C1 ~ }I
~1 Cl HOCH3
Cl C1 H~C~OCH3
O
H ~ c~3 Cl
H CF3 C1OC 2~5
O
R~N -
N~l R2
tert-C4Hg NH2 SCH3
tert-C4H~ N=CH-CH(CH3) 2 SCH3
~ NH2 CH3
- 34 -
0 . Z . 0050/033621
R~X~N ~ ~.3
R 1 N 0
CH3
H CH3 Br -CE-C~H5
H CH3 3r i-C3H7
~ c~3 Cl tert-C4Hg
H CH3 Cl C~\
O
O
, ~ .
R NC~2
02N ~0 - R
R2 R1
R R1 R2 R3
-C-CH3 sec C4H H H.
H CH3 H H~salts, esters )
H sec-C4H~3- H H(salts, esters )
-C-CH3 tert C4H9 H H
- 35 -
~3~
0 . Z . 0050/033621
n 3 tert-C 4E~9 E3: CH3
H i-G3H7 CH3 H ~alts, esters )
H tert-C4Hg H H ( salts)
o
~N~N R
J~,o
X O
CF3 3
H F CH3
~ 1~'
O . C~
~-s-~oC~3
~ ..
J'CH C2H5
H C
3 ~ N C~H5
o C2H5
- 36 -
0 . Z O 0050/033621
R - N 0
O l O
'~ _
Cl~ CX3
~J
Cl
~)~ CH3
i H7
3 ,.
0
.. ~ C~I3
tert; C4Hg-~N C0
o
~2
N <~
I 1 R2
R R.l R2 X
CH3 CH3 H ~3C~s_o
O
~H3 CH3 Br CX30S020
CH3 CH3 CH3 CH30S02-0
CH3 CH3 CH3 CF3-S02
O tC2H5
~C-NX O-C2H5
2 5
- 37 -
~3~
O . Z . 0050/03362~1
O n-C3~17
H3C>~ N~-O~CH2 C~=CH2
H3C
OH n-C3H7
H3 >(~-N~O-CH2-C~-C~I2
H3C -O-CH 3
ONa n C H
H3C~¢~G N O CHz CX CH2
H3C C O-CH
n 3
OH H.
~__~ Cl ~esters, salts)
NH2
Cl
Cl N COOH ~alts, ester
CF3
C~I3
.~ --N- C - CH 2-N~ \C 2 E5 ]
- 38
0 . Z . 0050/033621
~13C~N~4~N CH3] . 2CH30S03 (3
L ~2
/
2~
o <_C_CH2_N~N-CH2-C-~ 2CI(~)
~-CH3 0 _~-C~3
COOCX
C~Cl3
C~l Cl
COOC}~3
,, <~1 .
Cl
p~ . .
CN
CSNH;~
- 39 -
~L~3~
O.Z. 0050/033621
COOR
R~,R~
Rl~R2
H C1 NH2 C~ ~salts~ esters,
amides )
Cl Cl H C1 Na
H
C1 H C1 OCH3 H
Cl Cl H Cl (CH3)2N~2
Rl .
R O - C~ - C ~ O o R2
R R1 R2
~ .
_~ .
Cl~ )~ CX3 H (s&:~ts, esters, ami-des )
C1
C1~ H H " ,t .t
C1
fcl
C 1~ ~ H n tt rt
Cl
Cl~ H H ~ n n
.,
- 40 -
3~
O.Z. 0050~033621
C ~ CH3 ~ (salts, esters, amides)
Cl
Cl ~ c~3 ~ (salts, esters~ amides)
~H3
~ ~2 n 3
Cl ~ O (CH2)3 ~(salts, esters, amides)
o
Cl ~ O-(CX2)3-C-OH (salts, esters, amides)
CH3
C ~ -CH2-C-OH (salts, e~ters, amides)
-- -
Rl o
~,1 R2
OH CH3 Na
CH3 CH3 Na
CH3 CH3 OH
ONa c~3 Na
- 41 -
0 . Z . 0050/033621
Ps~ O
R N C CH2 ~ R
O O
,~CH3
~C -CH;2~ H~; CH 3
3 i-C3~-0-CH2 3
C~I3
~H3
CH CH -0-C;2H~ CH3
C 3H7 -NHCH 3
C~3
C~I-C=CH - O
N- C-CH2-0 -S -MH- i C3 7
~N C CH2 0 S 3 7
Ol-C -C~I2 -O-S -NH- C~ 3
o
~ n CH2 0-S-NH-i-C3H7
- 42 -
7~
.
O . Z . 0050/0~3621
CH~-C-OE~ ( salk s )
[~ =
( salts, esters )
HO COOE~
H - N--N
~ 2
<~S02~NH-S02CF3
c~3
HO~O
n
p -- CH2 ~ ~H ~ CH2 n ( salts)
HO
~1
N--N~3H7i
t~rt -C4Hg
(g>-S02NEI-C2X4-S ~ 3 7
C 3 7
~COONa
~COONa (and other salts)
- 43 -
3 ~L3
O.Z. 0050/033~2
~S~,S
H3C ~ N N CH3
O O
CH~ - CH2 - O - P ~ C - NH2 NHL~
NHCL~Ign
(,~,,OC 4Hgn
0 OC4Hgn,
n
P-CH2) N-CH2-C ;OH ( salts )
[~
~ (~) C1 (3
c~3
NH4SCN
O O
~S~CX3
0 ~0
~I4 Cg~ 3
OH
- 44 -
~IL3~
O.Z. 0050/033621
o
HN - C - CX
HN C - CH (salts)
CX3--N - NH - C GH2 ~ CX2 ~ COOH
CH~/ o
o
Cl GX ~H2
,
OH
[c~ 2-cH2-~-cx~ Cl~)
CH3
r Vc~ 1~
lC~ X2-P(c4Xg)3 ~
~(~ ClO
. .
H3C CH3
COOE~ ( salts ~ esters, amides )
- 45
O.Z. 0050/033621
HO ~ NH
~ NH
Ho_c.H2C~ ~
o
N - CH2 ~ C~ ~ Br
J oc~2-cH-cH~
N
N~,N
/
B ~
CH
Cl- ~ ~O-CH-CO~C-C~
It may also be useful to apply the new compounds, elther
alone or in combination with other herbicides, in admixture
wlth other crop protectlon agents, e.g., agents for combating
pests or phytopathogenic fungi or bacteria. The compounds may
also be mixed with solutlons o~ mineral matters used to remedy
nutrltional or trace element deficiencies. Oils o~ various types,
wetting agents, spreader-stickers and antifoams may also be
added to the lndividual active ingredients or mixtures thereof.
- 46 -
