Halogencyclopropyl compounds, and use as herbicidal agents

There are described new halocyclopropyl compounds of the general formula I ##STR1## in which R.sub.1, R.sub.2 and R.sub.3, independently of each other, are hydrogen or C.sub.1-4 -alkyl, PA1 X is hydrogen or halogen, PA1 Y is halogen, PA1 n is 0, 1, 2 or 3, PA1 U and V are hydrogen or halogen, and PA1 W is a heterocyclic group of formula ##STR2## in which T is halogen, C.sub.1-4 -alkyl, C.sub.1-4 -haloalkyl, CN or OR.sub.9 PA1 Q is CH or N, PA1 Z is O or S, PA1 R.sub.4, R.sub.5, R.sub.6, R.sub.7 and R.sub.8 are each a straight, branched or cyclic C.sub.1-7 -alkyl group optionally substituted by up to six halogen atoms, or PA1 R.sub.4 and R.sub.5, can also together form a 4 to 7 membered ring that is saturated or unsaturated and can contain further hetero atoms, such as O, S or N, and can optionally be substituted by one to three methyl groups or one to six halogen atoms, and PA1 R.sub.9 is hydrogen, C.sub.1-4 -alkyl or C.sub.1-4 -haloalkyl, processes for their preparation and their use as herbicide with high selectivity.

DESCRIPTION 
This invention relates to new halocyclopropyl compounds, their preparation 
by known methods and their use as herbicides. 
It is already known that certain tetrahydroindazoles and 
tetrahydrophthalimides have herbicidal properties (EP61 741 and 105 721). 
The activity of these substances in pre- and post-emergent use is good but 
they suffer from the disadvantage that their compatibility with several 
crops--such as for example cotton, soybeans and cereals is not sufficient. 
It has now been found that halocyclopropyl compounds of the general formula 
I 
##STR3## 
in which R.sub.1, R.sub.2 and R.sub.3, independently of each other, are 
hydrogen or C.sub.1-4 -alkyl, 
X is hydrogen or halogen, 
Y is halogen. 
n is 0, 1, 2 or 3. 
U and V are hydrogen or halogen, and 
W is a heterocyclic group of formula 
##STR4## 
in which T is halogen, C.sub.1-4 -alkyl, C.sub.1-4 -haloalkyl, CN or 
OR.sub.9 
Q is CH or N. 
Z is O or S. 
R.sub.4, R.sub.5, R.sub.6, R.sub.7 and R.sub.8 are each a straight, 
branched or cyclic C.sub.1-7 -alkyl group optionally substituted by up to 
six halogen atoms, or 
R.sub.4 and R.sub.5, can also together form a 4 to 7 membered ring that is 
saturated or unsaturated and can contain further hetero atoms, such as O, 
S or N, and can optionally be substituted by one to three methyl groups or 
one to six halogen atoms, and 
R.sub.9 is hydrogen, C.sub.1-4 -alkyl or C.sub.1-4 -haloalkyl, 
surprisingly posses outstanding compatibility with rice wheat, soybeans, 
maize, cotton and barley whilst at the same time showing improved 
herbicidal activity. 
The term "halogen" stands for F, Cl, Br or I. The expression haloalkyl 
means that one or more hydrogen atoms of the alkyl group are replaced by 
halogen. 
Examples of heterocyclic rings include: pyrrole, oxazole, thiazole, 
imidazole, pyridine, oxazine, thiazine, pyrimidine, pyrazine, triazine, 
oxadiazine and thiadiazine as well as their di-, tetra- or preferably 
hexahydroderivatives.

The compounds of the invention can be prepared in known manner according to 
the following routes: 
(a) A halide of the general formula II 
##STR5## 
in which R.sub.1, R.sub.2, R.sub.3, X, Y and n have the meanings given in 
formula I, and A is chlorine, bromine or iodine, is reacted with a phenol 
of formula III 
##STR6## 
in which U, V and W have the meanings given in formula I. 
(b) For the preparation of a compound of formula I, in which W is a 
4,5,6,7-tetrahydroindazol-2-yl group, a compound of formula IV 
##STR7## 
in which R.sub.1, R.sub.2, R.sub.3, X, Y, n, U and V have the meanings 
given in formula I, is reacted with a compound formula V 
##STR8## 
in which R.sub.10 is C.sub.1-4 -alkyl, C.sub.1-4 -haloalkyl or C.sub.1-4 
-alkoxy. 
The compounds of formula I, so obtained, in which T is hydroxy can be 
optionally further modified. For example, by reaction with dialkyl 
sulphate, compounds in which T is alkoxy can be obtained, and by reaction 
with a phosphoryl halide, compounds in which T is halogen can be obtained, 
which by treatment with NaCN can be optionally converted to the 
corresponding compound in which T is CN. 
(c) For the preparation of compounds of formula I, in which W is a 
2H-1,2,4-triazolin-3-on-2-yl group, a compound of formula IV 
##STR9## 
in which R.sub.1, R.sub.2, R.sub.3, X, Y, n, U and V have the meanings 
given in formula I, is reacted with a compound of formula VI 
##STR10## 
in which R.sub.4 and R.sub.5 have the meanings given in formula I and 
R.sub.11 is C.sub.1-4 -alkyl, or a compound of formula IV 
##STR11## 
in which R.sub.1, R.sub.2, R.sub.3, X, Y, n, U and V have the meanings 
given in formula I, is reacted with a keto acid of formula XII 
##STR12## 
in which R.sub.8 has the meaning given in formula I, to give a compound of 
formula XI 
##STR13## 
in which R.sub.1, R.sub.2, R.sub.3, X, Y, n, U, V and R.sub.8 have the 
meanings given in formula I, which is cyclised by treatment with a 
phosphoric acid ester azide to give a compound of formula XXIII 
##STR14## 
in which R.sub.1, R.sub.2, R.sub.3, X, Y, n, U, V and R.sub.5 have the 
meanings given in formula I, which is optionally reacted with a compound 
of formula X 
EQU R.sub.4 -A (X) 
in which R.sub.4 has the meaning given in formula I and A is chlorine, 
bromine or iodine. 
(d) For the preparation of the compound of formula I, in which W is a 
3H-1,3,4-oxdiazol-2-on-3-yl group, a compound of formula IV 
##STR15## 
in which R.sub.1, R.sub.2, R.sub.3, X, Y, n, U and V have the meanings 
given in formula I, is reacted with an acid derivative of formula VIII 
##STR16## 
in which R.sub.6 has the meaning given in formula I and R.sub.12 is 
halogen or C.sub.1-4 -alkoxy, to give, as an intermediate, a compound of 
formula VII 
##STR17## 
in which R.sub.1, R.sub.2, R.sub.3, X, Y, n, U, V and R.sub.6 have the 
meanings given in formula I, which is then reacted with phosgene or its 
reactive functional derivative. 
(e) For the preparation of compounds of formula I, in which W is a 
2H,4H-1,2,4-triazine-3,5-dion-2-yl group, a compound of formula IV 
##STR18## 
in which R.sub.1, R.sub.2, R.sub.3, X, Y, n, U and V have the meanings 
given in formula I, is reacted with a keto acid of formula XII 
##STR19## 
in which R.sub.8 has the meaning given in formula I, to give a compound of 
formula XI 
##STR20## 
in which R.sub.1, R.sub.2, R.sub.3, X, Y, n, U, V and R.sub.8 have the 
meanings given in formula I, which is cyclised by treatment with thionyl 
chloride or phosphoryl chloride and then with a carbamate ester to give a 
compound of formula IX 
##STR21## 
in which R.sub.1, R.sub.2, R.sub.3, X, Y, n, U, V and R.sub.8 have the 
meanings given in formula I, which is reacted with a compound of formula X 
EQU R.sub.7 -A (X) 
in which R.sub.7 has the meaning given in formula I and A is chlorine, 
bromine or iodine. 
(f) For the preparation of compounds of formula I, in which W is a 
4,5,6,7-tetrahydro-2H-1,2,3-triazolo[3,4-a]pyridin-8-ium-3-olat-2-yl 
group, a compound of formula XV 
##STR22## 
in which R.sub.1, R.sub.2, R.sub.3, X, Y, n, U and V have the meanings 
given in formula I, is diazotised with nitrous acid, reacted with 
piperidine-2-carboxylic acid and cyclised with acetic anhydride. 
(g) For the preparation of a compound of formula I, in which W is a 
1,3,4,5,6,7-hexahydro-2H-isoindole-1,3-dion-2-yl group, a compound of 
formula XV 
##STR23## 
in which R.sub.1, R.sub.2, R.sub.3, X, Y, n, U and V have the meanings 
given in formula I, is reacted with a compound formula XVI 
##STR24## 
in which Z=O or S. 
(h) For the preparation of compounds of formula I, in which W is a 
2,3,5,6,7,8-hexahydro-1H-imidazo[1,5-a]-pyridine-1,3-dion-2-yl or a 
2,3,5,6,7,8-hexahydro-1H-1,3,4-triazolo[1,2-a]pyridazine-1,3-dion-2-yl 
group, a compound of formula XV 
##STR25## 
in which R.sub.1, R.sub.2, R.sub.3, X, Y, n, U and V have the meanings 
given in formula I, is reacted with a compound of formula XVII or XVIII 
##STR26## 
in which Z=O or S, Q is CH or N and R.sub.15 is C.sub.1-4 -alkyl, or a 
compound of formula XIX 
##STR27## 
in which R.sub.1, R.sub.2, R.sub.3, X, Y, n, U, V and Z have the meanings 
given in formula I, is reacted with a compound of formula XX 
##STR28## 
in which Q is CH or N, Z=O or S and R.sub.15 is C.sub.1-4 -alkyl. 
The compound of formula XIX can be prepared by reacting a compound of 
formula XV 
##STR29## 
in which R.sub.1, R.sub.2, R.sub.3, X, Y, n, U and V have the meanings 
given in formula I, with phosgene or thiophosgene. 
(i) A compound of formula XXI 
##STR30## 
in which R.sub.1, R.sub.2, R.sub.3, U, V, W and n have the meanings given 
in formula I, is reacted with a halogenated methane derivative of formula 
XXII 
##STR31## 
in which X and Y have the meanings given in formula I, and B is hydrogen 
or 
##STR32## 
in which M is an alkali metal. 
The reaction according to process variant (a) is suitably carried out with 
the aid of acid acceptors at a temperature between 0.degree. and 
160.degree. C., especially between room temperature and the reflux 
temperature of the reaction mixture. Suitable acid acceptors include 
conventional bases, especially aliphatic amines, such as e.g. 
triethylamine or diisopropylamine, as well as alkali metal carbonates and 
their aqueous solutions. 
The etherification can also be carried out in a two phase system using a 
catalyst and optionally in the presence of a solvent. Suitable bases 
include alkali metal hydroxides and alkali metal carbonates, either in 
solid form or in aqueous solution. Suitable solvents are the reactants 
themselves if they are liquids. Otherwise, there can be used substances 
which are immiscible with water and inert to the bases, such as for 
example aliphatic or aromatic hydrocarbons, such as for example hexane, 
benzene or toluene. Preferred catalysts are crown ethers, such as e.g. 
1,4,7,10,13,16-hexaoxacyclooctadecane and quaternary ammonium salts, as 
described in Dehmlow and Dehmlow, Phase Transfer Catalysts, Weinheim 1980. 
Generally the starting materials are used in stoichiometric amounts. An 
excess of one or the other can be used in some cases but without any 
particular advantage. 
The reaction according to process variants (b) and (c) is generally carried 
out in the presence of a catalyst in a suitable solvent. The reaction 
temperature lies between 0.degree. and 150.degree. C., especially at the 
reflux temperature of the reaction mixture. Suitable solvents include for 
example dimethyl sulphoxide, halogenated hydrocarbons, such as for example 
methylene chloride and chloroform, aromatic hydrocarbons such as for 
example benzene, toluene, xylene, chlorobenzene and dichlorobenzene, as 
well as other solvents which are inert to the reactants, such as for 
example diethyl ether, tetrahydrofuran or dimethyl formamide. 
Example of catalysts are acids, such as acetic acid or sulphuric acid, as 
well as acidic ion exchange resins. 
The reaction according to process variant (d) is generally carried out with 
or without a suitable inert solvent. Suitable solvents include for example 
dimethyl sulphoxide, halogenated hydrocarbons, such as for example 
methylene chloride and chloroform, aromatic hydrocarbons such as for 
example benzene, toluene, xylene, chlorobenzene and dichlorobenzene, as 
well as other solvents which are inert to the reactants, such as for 
example diethyl ether, tetrahydrofuran or dimethyl formamide. 
The reaction of compounds of formula IX and compounds of formula X 
according to process variant (e) is suitably carried out with the aid of 
acid acceptors at a temperature between 0.degree. and 150.degree. C., 
especially between room temperature and the reflux temperature of the 
reaction mixture. Suitable acid acceptors include conventional bases, 
especially aliphatic amines such as e.g. triethylamine or 
diisorpropylamine as well as alkali metal carbonates and their aqueous 
solutions. 
The alkyation can also be carried out in a two phase system using a 
catalyst and optionally in the presence of a solvent. Suitable bases 
include alkali metal hydroxides and alkali metal carbonates, either in 
solid form or in aqueous solution. Suitable solvents are the reactants 
themselves if they are liquids. Otherwise, there can be used substances 
which are immiscible with water and inert to the bases, such as for 
example aliphatic or aromatic hydrocarbons, such as for example hexane, 
benzene or toluene. Suitable catalysts include crown ethers and quaternary 
ammonium salts. 
Generally the starting materials are used in stoichiometric amounts. An 
excess of one or the other can be used in some cases but without any 
particular advantage. 
The reaction according to process variant (f) is generally carried out in 
three stages without purification of the intermediates. Besides water 
there can be used as solvent any inert organic solvent. The reaction 
temperatures lie between -20.degree. and 100.degree. C., especially 
between -10.degree. C. and room temperature. 
The reaction according to process variants (g) and (h) is generally carried 
out at a temperature above 20.degree. C., e.g. at 100.degree. C. or at the 
reflux temperature of the reaction mixture. When one of the reactants is 
an anhydride, as with the compounds of formula XVI or XVII, the reaction 
is suitably carried out in the presence of an acid, such as acetic acid, 
for example in which acetic acid acts as solvent. It is however also 
possible for the reaction to take place in an inert solvent, such as e.g. 
dichloromethane or dimethyl sulphoxide, and to cyclise the intermediate 
addition product with an acid anhydride, such as for example acetic 
anhydride. 
The reaction according to process variant (h) with compounds of formula XIX 
and XX is generally carried out in an inert solvent at a temperature 
between 20.degree. C. and 150.degree. C., especially at the boiling point 
of the solvent. Suitable solvents are for example aliphatic and aromatic, 
optionally chlorinated, hydrocarbons, such as petroleum ether, benzene, 
toluene, xylene, dichloromethane, chloroform, tetrachloromethane, 
1,2-dichloroethane and chlorobenzene, as well as ethers, such as for 
example diethyl and di-n-butyl ether, methyl tert-butyl ether, 
tetrahydrofuran and dioxane, ketones, such as for example acetone, methyl 
ethyl ketone and methyl isopropyl ketone, as well as nitriles, such as 
acetonitrile and propionitrile, and sulphoxides, such as dimethyl 
sulphoxide or sulpholane. 
The reaction according to process variant (i) is generally carried out in a 
solvent which is inert to the reactants, such as chloroform, ethers, such 
as dioxane or diethylene glycol dialkyl ethers, aliphatic hydrocarbons, 
such as cyclohexane or decane, optionally under the influence of a strong 
base, such as an alkali metal alcoholate or hydroxide, preferably in a 2 
phase system in the presence of a phase transfer catalyst, such as those 
described in DEHMLOW AND DEHMLOW, Phase Transfer Catalysts, Weinheim 1980, 
at a temperature between room temperature and 200.degree. C., especially 
at the boiling point of the solvent. 
The compounds of the invention, prepared according to the above described 
processes, can be isolated in conventional manner, for example by 
distillation of solvent at normal or reduced pressure or by extraction. 
An increased level of purity can be achieved as a rule by column 
chromatography as well as by fractional distillation. 
The compounds of the invention are as a rule crystalline or viscous 
substances, which are to an extent highly soluble in halogenated 
hydrocarbons such as chloroform, sulphoxides, such as dimethyl sulphoxide, 
or esters, such as ethyl acetate. 
The compounds of the invention can contain one or more asymmetric C atoms, 
The present invention includes the optically active forms and mixtures 
thereof. In the examples, unless otherwise stated, the racemate is 
obtained. 
The starting materials of formula IV and XV can be obtained according to 
known processes. A possible synthesis route is shown in the following 
reaction scheme: 
##STR33## 
The preparation of the remaining starting materials is not described since 
they are known or can be obtained in an analogous manner to known 
processes. 
The present compounds according to the invention have an excellent 
herbicidal activity against economically important mono- and 
dicotyledonous weeds. It is immaterial whether the compounds are sprayed 
before sowing, pre-emerence or post-emergence. 
The compounds of the invention surprisingly possess outstanding 
compatibility with rice, wheat, soybeans, maize, cotton and barley. 
The compounds of the invention can, for example, be used for combating 
weeds of the following plant species: 
Dicotyledeonous weeds of the following families: Abutilon, Chrysanthemum, 
Brassica, Helianthus, Mentha, Sinapis, Lepidium, Galium, Stellaria, 
Anthemis, Chenopodium, Atriplex, Senecio, Portulaca, Ipomea, Matricaria, 
Galinsoga, Urtica, Amaranthus, Polygonum, Sesbania, Ambrosia, Sonchus, 
Solanum, Lamium, Veronica, Datura, Viola, Centaurea and Galeopsis; 
Monocotyledenous weeds of the following species: Avena, Alopecurus, 
Echinochloa, Setaria, Panicum, Digitaria, Poa, Eleusine, Brachiaria, 
Lolium, Bromus, Cyperus, Agropyron, Sagittaria, Cynodon, Monochoria, 
Fimbristylis, Eleocharis, Ischaemum and Apera. 
The use of the compounds of the invention is not limited to the weeds and 
crops mentioned above but can also be applied in a similar way to other 
plants. 
The compounds are suitable also for use in higher amounts for total weed 
control, for example, in industrial and railway installations and in roads 
and open spaces. The compounds can also be used to combat weeds in 
permanent cultivations, such as for example forests, ornamental tree, 
fruit tree, vines, citrus, nut, banana, coffee, tea, rubber, oil-palm, 
cocoa, berry-fruit and hop-plantations. 
The rates of use of the active material can very to a great degree. It 
depends essentially on the type of effect desired. In general, the 
quantities used lie between 0.01 and 5 kg of active material per hectare 
of land surface, preferably for example for combating weeds between 0.1 
and 0.5 kg of active material per hectare. 
When it is desired to broaden the spectrum of activity, other herbicides 
can also be added. Herbicidally active mixing partners suitable in this 
connection include for example, the active agents listed in Weed 
Abstracts, vol. 35, No. 3, 1986, under the heading "Lists of common names 
and abbreviations employed for currently used herbicides and plant growth 
regulators in Weed Abstracts". 
The designated active materials or their mixtures are suitably used in the 
form of preparations such as powders, dusts, granules, solutions, 
emulsions or suspensions, with the addition of liquid and/or solid 
carriers and/or diluents agents and if desired, binding, wetting, 
emulsifying and/or dispersing adjuvants. 
Suitable liquid carriers are, for example aliphatic and aromatic 
hydrocarbons, as well as cyclohexanone, isophorone, dimethyl sulphoxide, 
dimethylformamide and other mineral-oil fractions and plant oils. 
Suitable solid carriers include mineral earths, e.g. bentonite, silica gel, 
talcum, kaolin, attapulgite, limestone, silicic acid and plant products, 
e.g. flours. 
As surface-active agents there can be used for example calcium 
lignosulphonate, polyoxyethylenealkylphenyl ether, naphthalenesulphonic 
acids and their salts, phenolsulphonic acids and their salts, formaldehyde 
condensates, fatty alcohol sulphates, as well as substituted 
benzenesulphonic acids and their salts. 
The percentage of the active ingredient(s) in the various preparations can 
vary within wide limits. For example, the compositions can contain about 
10 to 90 percent by weight active ingredients, and about 90 to 10 percent 
by weight liquid or solid carriers, as well as, optionally up to 20 
percent by weight of surfactant. 
The agents can be applied in customary fashion, for example with water as 
the carrier in spray mixture volumes of approximately 100 to 1,000 l/ha. 
The agents can be applied using low-volume or ultra-low-volume techniques 
or in the form of so-called microgranules. 
The preparation of these formulations can be carried out in known manner, 
for example by milling or mixing processes. Optionally, individual 
components can be mixed just before use for example by the so-called 
commonly used tank-mixing method. 
Formulations can be prepared, for example, from the following ingredients. 
(a1) Wettable powder 
80% by weight, active material 
10% by weight, kaolin 
2% by weight, sodium N-methyl-N-oleyltaurine 
8% by weight, calcium lignosulphonate 
(a2) Wettable powder 
20% by weight, active material 
35% by weight, bentonite 
8% by weight, calcium lignosulphonate 
2% by weight, sodium N-methyl-N-oleyltaurine 
35% by weight, silicic acid 
(b) Paste 
45% by weight, active material 
5% by weight, sodium aluminium silicate 
15% by weight, mixed polymerisation product from cetyl polyglycol ether 
with 8 moles of ethylene oxide 
2% by weight, spindle oil 
10% by weight, polyethylene glycol 
23% by weight, water 
(c) Emulsifiable concentrate 
20% by weight, active material 
75% by weight, isophorone 
2% by weight, calcium dodecylbenzenesulphonate 
3% by weight, fatty alcohol polyglycol ether 
The following examples illustrate the preparation of compounds of the 
invention. 
Preparation Example 1 
N-[4-Chloro-5-(2,2-dichlorocyclopropylmethoxy)-2-fluorophenyl]-3,4,5,6-tetr 
ahydrophthalimide (Compound No 1.1) 
8.9 g (0.031 mol) 4-Chloro-2-fluoro-5-(2,2-dichlorocyclopropylmethoxy) 
aniline was dissolved in 12.5 ml acetic acid and 3.85 g 
3,4,5,6-tetrahydrophthalic anhydride added. The mixture was heated under 
reflux for 3 hours, then poured into ice-water and extracted with ether. 
The ether phase was neutralised with aqueous sodium hydrogen carbonate, 
washed with saturated brine, dried over magnesium sulphate and the solvent 
removed. The residue was chromatographed on silica gel using a mixture of 
9 parts hexane and 1 part ethyl acetate as eluent. 
7.8 g (=75% of theory) of brownish crystals, m.p. 121.degree.-122.degree. 
C., were obtained. 
The following compounds were prepared in an analogous manner: 
______________________________________ 
##STR34## 
Compound Physical 
No. R.sub.1 
R.sub.2 
R.sub.3 
n X Y U V Constant 
______________________________________ 
1.2 H H H 1 F F Cl F n.sub.D.sup.25 = 1.5375 
1.3 H H H 2 F F Cl F n.sub.D.sup.24 = 1.5280 
1.4 H H H 2 Cl Cl Cl F n.sub.D.sup.24 
______________________________________ 
= 1.5555 
Preparation Example 2 
2-[4-Chloro-5-(2,2-difluorocyclopropylmethoxy)-2-fluorophenyl]-4,5,6,7-tetr 
ahydro-(2H)-1,2,3-triazolo[3,4-a]pyridin-8-ium-3-olate (Compound No 2.1) 
4.6 g 4-Chloro-5-(2,2-difluorocyclopropylmethoxy)-2-fluoroaniline was 
suspended in a mixture of 9.7 ml concentrated sulphuric acid and 41.5 ml 
water and cooled to -10.degree. C. A solution of 1.38 g sodium nitrite in 
4.2 ml water was added dropwise at such a rate that the temperature of the 
reaction mixture did not rise above -5.degree. C. After the addition it 
was stirred for a further hour at -5.degree. C. and excess nitrous acid 
destroyed with urea until a test with iodine-starch paper was negative. 
The solution thus obtained was warmed to 0.degree. C. and added dropwise 
to an ice-cold solution of 2.3 g pipecolic acid and 8.3 ml triethylamine 
in 27.7 ml water. After the addition it was stirred for a further hour at 
0.degree. C. and the reaction mixture extracted several times with 
methylene chloride. The organic phases were combined, dried over magnesium 
sulphate and the solvent evaporated. The residue was taken up in 40 ml 
ether and treated with 4.14 ml acetic anhydride and 2.07 ml pyridine. The 
mixture was stirred overnight at room temperature, then poured into 
ice-water and extracted with ethyl acetate. The organic phases were dried 
over magnesium sulphate and the solvent evaporated. The residue was 
chromatographed on silica gel using 95 parts ethyl acetate and 5 parts 
methanol as eluent. 
0.9 g (=13.4% of theory) of crystals, m.p. 125.degree.-127.degree. C., were 
obtained. 
Preparation Example 3 
3-Chloro-2-]4-chloro-5-(2,2-difluorocyclopropylethoxy)-b 
2-fluorophenyl]-4,5,6,7-tetrahydro-2H-indazole (Compound No 3.1) 
5 g 4-Chloro-5-(2,2-difluorocyclopropylethoxy)-2-fluorophenylhydrazine was 
dissolved in 18 ml acetic acid, 2.85 ml ethyl cyclohexanone-2-carboxylate 
was added and the mixture heated under reflux for 8 hours. The mixture was 
then added to water and extracted with methylene chloride. The organic 
phases were neutralised with aqueous potassium hydrogen carbonate, washed 
with saturated brine and dried over magnesium sulphate. After evaporation 
of the solvent, there was obtained 8.4 g (=100% of theory) of crude 
product. This was treated with 3.6 ml phosphoryl chloride and the mixture 
heated under reflux. After 4 hours it was cooled, taken up in methylene 
chloride, washed with water and then saturated soda solution, dried over 
magnesium sulphate and the solvent evaporated. The residue was 
chromatographed on silica gel using a mixture of 95 parts dichloromethane 
and 5 parts methanol. 
2.6 g (=35.6% of theory) of a brown oil, refractive index n.sub.D.sup.25 
=1.5345, was obtained. 
The following compounds were prepared in an analogous manner: 
______________________________________ 
##STR35## 
Compound Physical 
No. R.sub.1 
R.sub.2 
R.sub.3 
n X Y U V Constant 
______________________________________ 
3.2 H H H 1 F F Cl F n.sub.D.sup.20 = 1.538 
3.3 H H H 1 Cl Cl Cl F n.sub.D.sup.25 = 1.5713 
3.4 H H H 2 Cl Cl Cl F n.sub.D.sup.25 
______________________________________ 
= 1.5615 
Preparation Example 4 
2-[4-Chloro-5-(2,2-difluorocyclopropylmethoxy)-2-fluorophenyl]-2,3,5,6,7,8- 
hexahydro-1,2,4-triazolo]4,3-a]pyridin-3-one (Compound No 4.1) 
3 g 4-Chloro-5-(2,2-difluorocyclopropylmethoxy)-2-fluorophenylhydrazine was 
dissolved in 40 ml xylene and 2.4 g ethoxycarbonyl-2-piperiodone and 1 g 
phosphorus pentoxide was added. The mixture heated under reflux for 3 
hours. It was then added to 100 ml water and the organic phase separated. 
The organic phase was neutralised with aqueous potassium hydrogen 
carbonate, dried over magnesium sulphate and the solvent removed. The 
residue was chromatographed on silica gel using ethyl acetate as eluent. 
1.2 g (=23% of theory) of an oil, refractive index n.sub.D.sup.25 =1.5438,, 
was obtained. 
The following compounds were prepared in an analogous manner: 
______________________________________ 
##STR36## 
Compound Physical 
No. R.sub.1 
R.sub.2 
R.sub.3 
n X Y U V Constant 
______________________________________ 
4.2 H H H 1 Cl Cl Cl F n.sub.D.sup.25 = 1.5655 
4.3 H H H 2 Cl Cl Cl F n.sub.D.sup.25 = 1.5620 
4.4 H H H 2 F F Cl F n.sub.D.sup.25 
______________________________________ 
= 1.5332 
Preparation Example 5 
2-[4-Chloro-5-(2,2-difluorocyclopropylmethoxy)-2-fluorophenyl]-3-thioxo-2,3 
,5,6,7,8-hexahydro-1H-imidazo[1.5-a]pyridin-1-one (Compound No 5.1) 
2.9 g 4-Chloro-5-(2,2-difluorocyclopropylmethoxy)-2-fluorophenyl 
isothiocyanate was dissolved in 20 ml hexane and added dropwise to a 
solution of 1.5 ml ethyl piperidine-2-carboxylate in 10 ml hexane. The 
mixture heated under reflux for 2 hours. The solvent was removed and the 
residue was chromatographed on silica gel using a mixture of 3 parts 
hexane and 1 part ethyl acetate. 
3.2 g (=82% of theory) of a viscous oil, refractive index n.sub.D.sup.40 
=1.54, was obtained. 
Preparation Example 6 
2-[4-Chloro-5-(2,2-difluorocyclopropylmethoxy)-2-fluorophenyl[-2,3,5,6,7,8- 
hexahydro-1H-imidazo[1,5-a]pyridine-1,3-dione (Compound No 6.1) 
In an analogous manner to preparation Example 5, by reaction of 8.33 g 
4-chloro-5-(2,2-difluorocyclopropylmethoxy)-2-fluorophenyl isocyanate and 
4.69 ml ethyl piperidine-2-carboxylate in 100 ml hexane, there was 
obtained 7.7 g (=66% of theory) of a semicrystalline, whose nmr spectrum 
is as follows: d=1.1-2.4 ppm (m) 9H, d=2.7-3.15 ppm (m) 1H, d=3.85-4.4 ppm 
(m) 4H, d=6.87 (d 6 Hz) 1H, d=7.3 (d 9 Hz) 1H. 
Preparation Example 7 
3-[4-Chloro-5-(2,2-difluorocyclopropylmethoxy)-2-fluorophenyl]-5tert-butyl- 
1,3,4-oxadiazolin-2-(3H)-one (Compound No 7.1) 
3 g 4-Chloro-5-(2,2-difluorocyclopropylmethoxy)-2-fluorophenylhydrazine 
hydrochloride was suspended in 18.5 ml toluene, treated with 3.6 ml 
triethylamine and the mixture stirred until the hydrochloride dissolved. 
Then, without cooling, 1.6 ml pivaloyl chloride was added slowly and the 
mixture stirred at room temperature for 2 hours. The reaction mixture was 
washed with water, saturated aqueous potassium bicarbonate and then again 
with water, dried over magnesium sulphate and the solvent removed. There 
remained, as a residue, 3.7 g of a red oil, that besides impurities, 
contained 
N'-[4-chloro-5-(2,2-difluorocyclopropylmethoxy)-2-fluorophenyl]pivaloylhyd 
razide. This crude product was dissolved in 22 ml of a 20% solution of 
phosgene in toluene, heated slowly to 100.degree. C. and kept at this 
temperature for 3 hours. It was then cooled, treated with 20 ml methanol 
and concentrated. The residue was taken up in methylene chloride, washed 
twice with potassium bicarbonate and once with water, dried over magnesium 
sulphate and concentrated. To purify it, the crude product was 
chromatographed on silica gel using hexane/ethyl acetate=4:1 as eluent. 
1.2 g (=24.5% of theory) of product, refractive index n.sub.D.sup.20 
=1.5082, was obtained. 
Preparation Example 8 
N-[4-Chloro-5-(2,2-difluorocyclopropoxy)-2-fluorophenyl]-3,4,5,6-tetrahydro 
phthalimide (Compound No 8.1) 
1.2 g N-[4-Chloro-2-fluoro-5-vinyloxyphenyl)-3,4,5,6-tetrahydrophthalimide 
was dissolved in 5 ml diethylene glycol dimethyl ether, the mixture was 
heated to reflux and a solution of 2.8 g sodium chlorodifluoroacetate in 5 
ml diethylene glycol dimethyl ether was added slowly. The mixture was 
heated under reflux for 5 hours, then separated from the sodium chloride, 
which formed, and the solvent removed. The residue was chromatographed on 
silica gel using a mixture of hexane/diethyl ether=1:1. 
0.6 g (=43% of theory) of a crystalline substance, m.p. 
105.degree.-107.degree. C., was obtained. 
Preparation Example 9 
1-[4-Chloro-5-(2,2-difluorocyclopropylmethoxy)-2-fluorophenyl]-4-difluorome 
thyl-3-methyl-1,2,4-triazolin-5-(4H)-one (Compound No 9.1) 
8.2 g 4-Chloro-5-(2,2-difluorocyclopropylmethoxy)-2-fluorophenylhydrazine 
hydrochloride was dissolved in 163 ml water, treated first with 81 ml 
ethanol and then dropwise with a solution of 2.75 ml pyruvic acid in 81 ml 
water. The mixture was stirred for 1 hour and the precipitated product 
filtered and dried. There was obtained 7.9 g of the still slightly impure 
hydrazone that was used in this form. 
The hydrazone was dissolved in 130 ml toluene, treated with 3.3 ml 
triethylamine and heated until the solution became clear. It was then 
cooled to ca. 35.degree. C., 5.1 ml diphenyl phosphorazidate added 
dropwise and the mixture heated slowly to 75.degree. C. It was maintained 
at this temperature until no more nitrogen evolved and then heated to 
reflux. After 12 hours it was cooled, washed three times with 10% soda 
solution, the aqueous phase washed twice with toluene and acidified. The 
product was extracted with toluene and the organic phase dried. After 
removal of the solvent, the product was chromatographed on silica gel 
using ethyl acetate as eluent. There was obtained 3.7 g (=35% of theory) 
of 1-[4-chloro-5-(2,2-difluorocyclopropylmethoxy)-2-fluorophenyl]-3-methyl 
-1,2,4-triazolin-5-(4H)-one 
The product, obtained from above, was dissolved in 300 ml cyclohexane, 
treated with 2.7 g potassium hydroxide and 2 g tetrabutylammonium bromide, 
the mixture heated to reflux and then chlorodifluoromethane passed in. 
After the reaction had finished (as shown by thin layer chromatography) 
the solution was decanted, washed twice with each of 1N hydrochloric acid 
and 10% aqueous soda, dried over magnesium sulphate and concentrated. The 
residue was chromatographed on silica gel with ethyl acetate and then once 
with methylene chloride. 
80 mg (=2% of theory) of product, refractive index n.sub.D.sup.40 =1.535, 
was obtained. 
Preparation of some starting materials 
Preparation of 
4-chloro-5-(2,2-difluorocyclopropylmethoxy)-2-fluoronitrobenzene 
3.6 g 2-Chloro-4-fluoro-5-nitrophenol was dissolved in dimethylformamide 
and treated with potassium carbonate. The mixture was stirred at room 
temperature for one hour and then 3.3 g 2,2-difluorocyclopropylmethyl 
bromide added. It was the heated at 80.degree. C. for 2 hours and added to 
water. The mixture was extracted with methylene chloride and the organic 
phase washed with saturated brine, dried over magnesium sulphate and 
concentrated. The residue was chromatographed on silica gel using a 
mixture of 3 parts hexane and 1 part ethyl acetate. There was obtained 5 g 
(=93% of theory) of yellow crystals whose nmr spectrum is as follows: 
.delta.=1.1-2.4 ppm (m) 3H, .delta.=4.15 ppm (d 7 Hz,tr 1.5 Hz) 2H, 
.delta.=7.35 ppm (d 10 Hz) 1H, .delta.=7.5 ppm (d 7 Hz) 1H. 
The following compounds were prepared in an analogous manner: 
______________________________________ 
##STR37## 
R.sub.1 
R.sub.2 
R.sub.3 X Y n U V 
______________________________________ 
H H H F F 2 Cl F 
H H H Cl Cl 1 Cl F 
H H H Cl Cl 2 Cl F 
______________________________________ 
Preparation of 4-chloro-2-fluoro-5-(2,2-difluorocyclopropylmethoxy)aniline 
36.9 g 4-Chloro-2-fluoro-5-(2,2-difluorocyclopropylmethoxy)nitrobenzene in 
600 ml ethanol was hydrogenated by the addition of 5 g of 10% palladium 
metal on activated charcoal at room temperature and normal pressure. After 
the uptake of hydrogen is complete the catalyst is filtered off, the 
solvent evaporated to give 29.3 g(=89% of theory) of an oil, whose nmr 
spectrum is as follows: .delta.=1.1-2.2 ppm (m) 3H, .delta.=4.0 ppm (d 10 
Hz wide) 2H, .delta.=5 ppm (s wide) 2H, .delta.=6.5 ppm (d 7 Hz) 1H, 
.delta.=7.0 ppm (d 10 Hz) 1H. 
The following compounds were prepared in an analogous manner: 
______________________________________ 
##STR38## 
R.sub.1 
R.sub.2 
R.sub.3 X Y n U V 
______________________________________ 
H H H F F 2 Cl F 
H H H Cl Cl 1 Cl F 
H H H Cl Cl 2 Cl F 
______________________________________ 
Preparation of 
4-chloro-2-fluoro-5-(2,2-difluorocyclopropylmethoxy)phenylhydrazine 
29.3 g 4-Chloro-2-fluoro-5-(2,2-difluorocyclopropylmethoxy)aniline was 
treated first with 45 ml half concentrated hydrochloric acid and then with 
273 ml concentrated hydrochloric acid. It was then cooled to -10.degree. 
C. and treated dropwise with a solution of 8.3 g sodium nitrite in 17 ml 
water at a such rate that the temperature of the reaction mixture did not 
rise above -5.degree. C. It was stirred for 3 hours at -5.degree. C. and 
the at -15.degree. C., a solution of tin (II) chloride dihydrate in 34 ml 
concentrated hydrochloric acid added dropwise at such a rate that the 
temperature of the reaction mixture did not exceed -10.degree. C. It was 
warmed at room temperature overnight. For the work-up, it was cooled to 
0.degree. C. and slowly neutralised with with 430 ml 32% caustic soda 
solution. The precipitated tin hydroxide slurry was separated by 
filtration through Celite and the filter cake washed with ether and the 
aqueous mother liquor extracted with ether. The combined organic phases 
were dried over magnesium sulphate and the solvent removed. 
26 g(=100% of theory) of an oil is obtained, whose nmr spectrum is as 
follows: .delta.=1.1-2.3 ppm (m) 3H, .delta.=4.0 ppm (d 8 Hz wide) 2H, 
.delta.=6.85 ppm (d 7 Hz) 1H, .delta.=7.0 ppm (d 10 Hz) 1H. 
The following compounds were prepared in an analogous manner: 
______________________________________ 
##STR39## 
R.sub.1 
R.sub.2 
R.sub.3 n X Y U V 
______________________________________ 
H H H 2 F F Cl F 
H H H 1 Cl Cl Cl F 
H H H 2 Cl Cl Cl F 
______________________________________ 
The following examples illustrate the activity of the compounds of the 
invention: 
Use Example A 
In the greenhouse, the compounds of the invention at a rate of 1 kg of 
active material per hectare, emulsified in 500 liters of water per 
hectare, were sprayed on the test plant species Matricaria and Viola in 
pre- and post-emergency treatments. 3 weeks after the treatment the 
results were appraised. All the compounds of the preparation Examples 1 to 
9 caused destruction of the plants based on a scheme where 0=no activity 
and 4=destruction. 
Use Example B 
In the greenhouse, the listed plants were treated preemergently with the 
listed compounds at a rate of 0.1 kg of active material per hectare. For 
this purpose, the compounds were sprayed evenly over the plants as an 
emulsion in 500 liters of water per hectare. 3 weeks after the treatment, 
the compounds of the invention in comparison with known materials showed a 
high selectivity with excellent activity against the weeds. 
__________________________________________________________________________ 
Compound 
Br 
So 
Go 
Gl St 
Ab 
Ma Vi 
Av Al 
Ec 
Se 
Cy 
__________________________________________________________________________ 
No 4.1 
4 4 0 0 4 4 4 4 4 4 4 4 4 
Comparison agents 
EP 61 741 
No 1 2 3 1 1 3 3 4 4 2 2 2 4 1 
EP 105 721 
No 1 3 4 2 1 3 4 4 4 2 3 4 4 0 
Oxadiazon 
0 3 0 0 2 3 2 4 0 2 1 3 0 
__________________________________________________________________________ 
Assessment scheme 
0=no activity 
1=slight damage 
2=intermediate damage 
3=heavy damage 
4=total destruction 
Species 
Br=Brassica sp. 
So=Solanum sp. 
Go=Gossypium hirsutum 
Gl=Glycine max. 
St=Stellaria media 
Ab=Abutilon hybridum 
Ma=Matricaria chamomilla 
Vi=Viola tricolor 
Av=Avena fatua 
Al=Alopercurus myosuroides 
Ec=Echinochloa crus-galli 
Se=Setaria italica 
Cy=Cyperus esculentus 
Use Example C 
In the greenhouse, the listed plants were treated postemergently with the 
listed compounds at a rate of 0.3 kg of active material per hectare. For 
this purpose, the compounds were sprayed evenly over the plants as an 
emulsion in 500 liters of water per hectare. 3 weeks after the treatment, 
the compounds of the invention in comparison with known materials showed a 
high selectivity with excellent activity against the weed. 
__________________________________________________________________________ 
Compound 
Br 
So 
Gl 
He 
St 
Ab 
Ma Vi 
Ch 
Ip 
Ze 
Tr 
Ho 
Or 
Sr 
Se 
__________________________________________________________________________ 
No 1.1 
4 4 0 4 4 4 4 4 4 4 0 0 0 0 0 3 
No 3.1 
4 4 0 4 2 2 4 3 4 3 0 0 0 0 0 4 
No 3.2 
4 4 0 3 4 3 4 4 4 4 0 0 0 0 0 4 
No 3.4 
2 3 0 3 1 1 2 3 3 2 0 0 0 0 0 1 
No 4.3 
3 4 0 3 3 4 4 3 4 4 0 0 0 0 0 3 
Comparison 
agent 
Oxadiazon 
4 4 4 2 2 3 3 4 3 4 2 2 2 2 2 4 
__________________________________________________________________________ 
Assessment scheme 
0=no activity 
1=slight damage 
2=intermediate damage 
3=heavy damage 
4=total destruction 
Species 
Br=Brassica sp. 
So=Solanum sp. 
Go=Gossypium hirsutum 
Gl=Glycine max. 
He=Helianthus annus 
St=Stellaria media 
Ab=Abutilon hybridum 
Ma=Matricaria chamomilla 
Vi=Viola tricolor 
Ch=Chrusanthemum segetum 
Ip=Ipomoea purpurea 
Ze=Zea mays 
Tr=Triticum aestivum 
Ho=Hordeum vulgare 
Or=Oryza sativa 
Sr=Sorghum sativum 
Se=Setaria italica 
Use Example D 
In the greenhouse, the listed plants were treated postemergently with the 
listed compounds at a rate of 0.3 kg of active material per hectare. For 
this purpose, the compounds were sprayed evenly over the plants as an 
emulsion in 500 liters of water per hectare. 3 weeks after the treatment, 
the compounds of the invention showed good herbicidal properties. 
______________________________________ 
Compound Ec Ce Cd Fi 
______________________________________ 
No 1.1 1 2 3 4 
No 1.2 4 2 4 4 
No 3.2 4 1 3 4 
No 4.3 3 1 3 4 
No 4.4 4 3 4 4 
No 5.1 1 1 3 3 
No 6.1 4 4 4 4 
______________________________________ 
Assessment scheme 
0=no activity 
1=slight damage 
2=intermediate damage 
3=heavy damage 
4=total destruction 
Species 
Ec=Echinochloa crus-galli 
Cy=Cyperus esculentus 
Cy=Cyperus difformis 
Fi=Fimbrystylis miliacea 
Use Example E 
In the greenhouse, the compounds listed in the table were applied at rates 
also given in the table. For this purpose, the compounds were applied in 
containers with 1500 ml water (water application) The test plants were 
treated at the 2 to 5 leaf stage. Three weeks after the application, the 
damage to the plants was assessed. 
As the table shows, the compounds of the invention are very active against 
important weeds of rice. 
______________________________________ 
Water application 
Compound ppm Ec Ce Cd Fi Sa El 
______________________________________ 
No 3.2 10 4 1 3 3 -- -- 
No 4.3 10 4 1 4 4 -- -- 
No 4.4 1 4 3 4 4 -- -- 
3 4 3 4 4 -- -- 
No 5.1 1 4 2 2 2 -- -- 
3 4 4 3 4 -- -- 
No 6.1 1 4 4 4 4 -- -- 
3 4 4 4 4 -- -- 
No 7.1 3 4 -- 4 -- 3 4 
No 8.1 3 4 -- 4 -- 3 4 
No 9.1 3 4 -- 4 -- 3 4 
______________________________________ 
Assessment scheme 
0=no activity 
1=slight damage 
2=intermediate damage 
3=heavy damage 
4=total destruction 
-=not tested 
Species 
Ec=Echinochloa crus-galli 
Cy=Cyperus esculentus 
Cy=Cyperus difformis 
Fi=Fimbrystylis miliacea 
Sa=Sagittaria pusilla 
El=Eleocharis acicularis