CA1094573A

CA1094573A - Herbicidal and fungicidal agents

Info

Publication number: CA1094573A
Application number: CA281,281A
Authority: CA
Inventors: Gerhard Horlein; Werner Becker; Peter Langeluddeke; Helmut Kocher; Burkhard Sachse
Original assignee: Hoechst AG
Current assignee: Hoechst AG
Priority date: 1976-06-24
Filing date: 1977-06-23
Publication date: 1981-01-27
Also published as: GB1579201A; AU2639677A; EG12743A; BR7704047A; FR2355799A1; AU510762B2; OA05687A; FR2355799B1; ZA773766B; ES459862A1; PL199094A1; DE2628384A1; GR74113B; PL106885B1; AT354803B; IL52372A0; JPS6113458B2; DE2628384C2; IE45009B1; IE45009L

Abstract

ABSTRACT OF THE DISCLOSURE
Compounds of the formula I

(I) in which R represents-halogen, CF3, (C1-C4)-alkyl, or nitro, R1 represents hydrogen, halogen, or (C1-C4) alkyl, n is 1 to 3, n1 is 0 to 3, X is -O- or -CH2-, Y is 0, S, or NH and Z represents a cyanoethyl group or a radical of the formula

Description

lOo<.~

~his invention provides a compound of the general formula ~ ~ O-CH-C-Y-Z (I) R(n) Rl(nl) in which n represents an integer from 1 to 3, nl represents an integer from 0 to 3, and n and nl rnay be the same or different, R represents a halogen atam, CF3, (Cl-C4)-aIkyl, or nitro, Rl represents hydrogen, a halogen atom, or (Cl-C4)-aIkyl, and any two or more of the R and Rl moieties may be the same or different, X represents -0- or -CH2-, Y represents -O-, -S- or -NH- and Z represents a cyanoethyl group or a radical of the general formula -A-CI-OR3~
b in which A represents a methylene group which.r,~ay be unsubstituted or substituted by -CH3, -C2H5, -COCH3 or by another radical of the general formula -COOR'3, or a phenylene or styryl radical which radicals rnay be unsubstituted or substituted in the ring by one lOg~ 1573 or two of the same or different substituents selcctcd from halogen atoms and (Cl-C4)-alkyl and nitro groups, and R3 and R'3, which may be the same or different, each rep-resents a (Cl-C4)-alkyl group.
Preferred compounds of the general formula I are those in which a halogen is chlorine and/or bromine, alkyl groups or moieties are those having 1 or 2 carbon atoms, n = 1 or 2, nl = O and Y represents an oxygen atom.
Especially preferred are compounds in which (R)n rep-resents 4-Cl, 2,4-Cl, 4-Br, 2-Cl, 4-Br or 4-CF3, nl = O and X and Y represent oxygen atoms. Z preferably represents a cyanoethyl group, e.g. the 2-cyanoethyl group, or a radical of the general formula -A-COOR3, in which A = -CH2-, -CH(CH3)-or -CH(C2H5)-.
The invention also provides a process for the preparation of a compound of the general formula I, which comprises reacting a) a compound of the general formula R)~_ X -~-O-CH-C-YII ~Il) in which n, nl, R, Rl, X and Y have the meanings given above, or an alkali metal or ammonium salt thereof with 10~3 a compound of the general formula Hal-Z (III) in which Z has the meaning given above and Hal represents a halogen atom, or b) a compound of the general formula ~ -X- ~ - 0-CH-C-Hal ~IV) R (n) (nl ) in which n, nl, R, Rl, X and Hal have the meanings given above, with a compound of the general formula HYZ (V) in which Y and Z have the meanings given above, or an alkali metal or ammonium salt thereof, optionally in the presence of an acid-binding agent.
In the formulas II and III, Hal preferably represents a chlorine or bromine atom.
Compounds of the general formula I have herbicidal pro-perties, exhibiting a good action against a broad spectrum of weeds in both pre-emergence and post-emergence treatment.

Thus, compounds of this invention may be used to combat, for example, grass-type weeds such as oat grass (Avena), foxtail grass lAlopecurus), rye-grass ~Lolium) and bristle-grass, hen-grass and crab-grass (Setaria, Echinocloa and Digitaria), in dicotyledonous crop plants.
With some of the compou~s it is possible to control selectively even grass-type weeds in cereals.
Even when high doses are applied, soya beans, peanuts, dwarf beans, field beans, peas, lucerne, flax, cabbage, rape, cucumber, sunflower, tobacco, carrots, celery and sugar beet are generally not damaged.
As a result of their specific action against weeds, especially wild oats, foxtail-grass, rye-grass and millet-grass, a compound of the present invention may be used in fields strongly affected by weeds in preference to a number of the successful known herbicidal agents such as, for example, Alachlor, Monolimuron, Linuron, Pyrazon, Phenmedipham, sodium trichloroacetate, Fluorodifen and Mecoprop.
Further, the quantity necessary for the complete des-truction of the weeds is generally far lower than in the case of the above-mentioned known herbicides.
An additional advantage of compounds of the present invention is their low toxicity to warm-blooded animals.
Accordingly, the present invention provides a method of combating weed grasses, which comprises applying the com-pound of the invention to the weed grass or to the area or soil infested with, or liable to infestation by, a weed grass.
Surprisingly, compounds of the formula I also exhibit good action against harmful fungi on commercially valuable ~0'~ ~;73 materials as well as against phytopathogenic fungi, such as, for example, Piricularia oryzae, rust fungus, Botrytis cinerea, Plasmopara viticola, Phytophthora infestans, true types of mildew, Rhizoctonia solani, Septoria nodorum, Ustilago nuda, Phoma betae, Pythium ultimum and Helminthosporium gramineum.
Accordingly, the present invention also provides a me~hod of combating fungal infections, which comprises applying a compound of the invention to the fungus or to an object, material or area infected with, or liable to infection with, a fungus.
For application as fungicide to a commercial substrate, the compound may be used, for example, as an additive to lacquers, varnishes and paints.
For use as protective agent for plants the compound may be formulated as a dust, spray powder, dispersion or emulsion concentrate. The total content of active substance is gener-ally, depending on the formulation, from 2-80% by weight.
In addition they may contain the usual adhesives, wetting agents, dispersing agents, fillers and carriers. They may also be mixed with other fungicides.
The invention therefore also provides a herbicidal and/or fungicidal preparation, which comprises a compound of the general formula I and a suitable carrier therefor.
The herbicidal or fungicidal preparation may contain one or more customary formulation auxiliaries and inert substances and generally contains from 2 to 95% by weight of the active substance of formula I. The preparation may, for example, be ~I.O~ ~S73 in the form of a wettable powder, emulsifiable concentrate, sprayable solution, dusting agent or granulate.
A wettable powder is a preparation uniformly dispersible in water, and in addition to the active substance contains, apart from a diluent or inert substance, a wetting agent, for example a polyoxethylated alkyl phenol, a polyoxethylated oleyl or stearyl amine, or an alkyl or alkylphenyl sulphonate and a dispersing agent, for example the sodium salt of ligninsul-phonic acid, 2,2'dinaphthylmethane-6,6'-disulphonic acid or f oleoylmethyltaurine acid.
An emulsifiable concentrate may be ob~ained by dissolving the active substance in an organic solvent, for example, butanol, cyclohexanone, dimethylformamide, xylene or an aromatic substance having relatively high boiling point.
A dusting agent or sprayable powder may be obtained by grinding the active substance with a finely divided solid substance, for example talcum or a natural clay, such as kaolin, bentonite, pyropyhllite or diatomaceous earth.
A sprayable solution, us~ed widely in spray cans, contains the active substance dissolved in an organic solvent, and in addition, for example, as propellant, a mixture of fluorochloro-hydrocarbons and/or carbon dioxide.
A granulate may be prepared either by spraying the active substance on to adsorptive, granulated inert material, or by applying the active substance concentrate by means of an adhesive, for example polyvinyl alcohol, or the sodium salt of polyacrylic acid, or a mineral oil, to the surface of a carrier 10~4573 substance, e.g. sand, kaolinite or granulated inert material.
Alternatively, suitable active substances may be formulated in the manner usual for the production of manure granules, if desired in admixture with manure.
The concentration of the active substance in the herbi-cidal preparation may vary according to the formulation. In a wettable powder, the concentration of active substance may vary, for example, from 10 to 80%, the remainder consisting of the above-mentioned formulation additives. In an emulsifiable concentrate, the concentration of active substance may be from 10 to 80%. A dusting agent usually contains from 5 to 20%
of active substance, and a sprayable solution from 2 to 20%.
The content of active substance in a granulate depends to some extent on whether the active compound is liquid or solid and on the choice of granulating auxiliary, filler and other material.
For application, the commercially customary concentrate may, if necessary, be diluted in the usual manner, for example by means of water in the case of a wettable powder or emulsi-fiable concentrate. Dusting agents, granulated preparations and sprayable solutions are generally not diluted with further inert substances before use. The quantity required for appli-cation varies depending on the external conditions such as temperature and humidity, and may vary, for example, from 0.1 kg/ha to 10 kg/ha of active substance, but is preferably from 0.1 to 3 kg/ha. The active substance according to the inven-tion may be combined with one or more other herbicides and/or soil insecticides.

The following Examples illustrate the invention.
PREPARATION EXAMPLES
Example 1

2-~4'(4"-Chlorophenoxy)-phenoxy~-propionyllactic acid methyl ester A solution of 81 grams of 2- ~4'(4"-chlorophenoxy)-phenoxy]-propionic acid and 48 grams of 2-bromopropionic acid methyl ester in 160 ml of acetone was heated at the boil for 8 hours, while stirring, with 40 grams of potassium carbonate.
After cooling to 20C the inorganic salts were filtered off.
The acetone was distilled off from the filtrate and the residue was distilled in vacuo.
91 grams (87% of the theoretical yield) of the following compound having a Bpo 1 : 190 - 191C were obtained.

Cl - ~ - O - ~ -O-CH-C-O-CH-C-OCH3 Example 2 2- L4'(2",4"-Dichlorophenoxy)-phenox~ -propionylglycolic acid methyl ester 61 grams of 2-~4'-(2",4"-dichlorophenoxy)-phenoxy] -propionic acid and 24 grams of chloracetic acid methyl ester were dissolved in 200 ml of butanone. After adding 26 grams of potassium carbonate, the mixture was heated at the boil for 8 hours while stirring. The reaction mix~ure was cooled to _ g _ ~0~573 20C and the inorganic salts were filtered off. The butanone in the filtrate was distilled off and the ester formed was purified by vacuum distillation.
67 grams ~90.0% of the theoretical yield) of the following compound having a Bpo 05 : 207 - 208C were obtained.

Cl~O-~-O-CH-C-O-CH2-C-OCH3 ~ O O
Cl Example 3 2-~4'-(2",4"-Dichlorophenoxy)-phenoxy~ -propionylthioglycolic acid methyl ester 48 grams of thioglycolic acid methyl ester were dissolved in 200 ml of toluene. At a temperature of 20 to 40C, 156 grams of 2-~4'-(2",4"-dichlorophenoxy)phenoxy~-propionic acid chloride, dissolved in 150 ml of toluene, and 48 grams of dry triethylamine, dissolved in 50 ml of toluene, were added drop-wise simultaneously. The mixture was then stirred for 2 hours at 40C. The triethylamine chlorohydrate formed was suction filtered. The toluene in the filtrate was distilled off and the residue was purified by distillation at 0.2 torr.
180 grams (96% of the theoretical yield) of the follow-ing compound having a Bpo 2 : 230 - 232C were obtained.

Cl- ~ 0- ~ O-CH C~-S-CH2-1CI-OC~3 109~573 Example 4 2-~4'-(4"-Bromophenoxy)-phenoxy~-propionic acid 2-cyanoethyl ester 30 grams of 3-hydroxypropionic acid nitrile were dissolved in 150 ml of toluene. At a temperature of 20 to 40C, 143 grams of 2-[4'-(4"-bromophenoxy)-phenoxy]-propionic acid chloride, dissolved in 100 ml of toluene, and 40 grams of dry triethyl-amine, dissolved in 50 ml of toluene, were simultaneously added dropwise. The mixture was then stirred for 2 hours at 40C, cooled to 20C, suction filtered and the toluene was distilled off from the filtrate. 151 grams of residue were obtained.
Distillation of the residue yielded 138 grams (88% of the theoretical yield) of the following compound having a Bpo 1 :
208 - 210C.

Br-~-O- ~-O-CH-C-O-CH2-CH2 -C_N

Example 5 2-t4'-~4"-Trifluoromethylphenoxy)-phenoxy~-propionic acid 4-methoxycarbonyl henyl ester P .
23 grams of 4-hydroxybenzioc acid methyl ester and 17 grams of dry triethylamine were dissolved in 120 ml of toluene.
At 20 to 40C a solution of 52 grams of 2- E'-(4"-trifluoro-methylphenoxy)-phenox~ -propionic acid chloride in 80 ml of toluene was added dropwise. After the mixture had been stirred at 40C for 2 hours~ it was cooled to 20C, triethylamine 10~4573 clllorohydrate was filtered off with suction and the toluene was distilled off from the filtrate. The oil obtained was recrystallised from n-hexane.
64 grams (92% of the theoretical yield) of the following compound having a melting point of 78 - 79C were obtained.

~ ~ -0-CH-C-O- ~ -IC-O-CH3 Example 6 2-14'-(2",4"-Dichlorophenoxy)-phenoxy~-propionyloxy (2-aceto-acetic acid methyl ester) 70 grams of the sodium salt of 2- L4'-(2",4"-dichlorophenoxy)-phenoxy3 -propionic acid were suspended in 300 ml of benzene and 32 grams of 2-chloracetoacetic acid methyl ester were added. Stirring was carried out at 80C for 8 hours then the mixture was cooled and sodium chloride was filtered off. The toluene was removed by distillation.
76 grams of yellow oil having a refractive index of nD25 = 1.5593 were obtained.

Cl- ~ -0- ~ -0-CH-C-0-CH-C-0-CH3 Cl CH3 The compounds listed in the following Tables were prepared in accordance with the processes in Examples 1 to 6.

Table 1: 10~ ~3 -o- ~ -O-CH-C-O-A-C-OR3 O O

R(n) Rl (nl) I: A = -CH(CH3)-Example R(n) 1(nl) 3 BP~
.. _ ... .
7 4-Cl H CH3 Bp, 190 - 191 8 2,4-Cl H CH3 0.1' 9 3,4-Cl H CH Po.ol: 188 - 190 11 2-Cl,4-Br H CH3 pO l196 - 198 12 4-CF3 H CH PQ.05198 - 200

3 ~ 3-CE~ j H ¦ CH3 pO ~~82 185 16 3-CF3,4-C1 ~ CH B ~1 7 ! 2-Cl l ¦ CH3 ¦ Bp 5-86 - 87 19 3-Cl,4-CH~ H CH3 ~0.11~32 - 184

4-Cl 3-CH3 CH3 Bp :190 191 2l2 2,4-Cl 3-CH3 CH3 Po,05: 194 196 23 2,4-C1 H 2 5 Po 1194 - 196 24 2-Cl,4-Br H 2 5 Po 1198 - 200 2 5 p~ ~:199 - 200 2-Cl,4-CF3 H C2H5 B

27 4-CF3 - H C H Po 05185 _ 87 2 5 Po.2204 - 206 ~O~i~573 Table 1 (continued) Example r I ~ nl ~ ~3 P(C) 28 3,4-Cl H -C H B
2 5 Po.l: 201 - 202 29 2-Cl H 2 5 Po 05194 - 195 4-Cl H ~CH3 Po 2183 - 184 31 2,4-Cl H ~CH3 Po.l'185 - 186 32 3,4-Cl H ~CH3 Po 1191 - 194 332-Cl,4-Br H C~-CH3 34 4-Br H ~CH3 Po 1198 199 4-C~3 H ~CH Po 1187 - 188 36 2,4-Cl 3-CH3CH~CH3 Po.l:188 - 189 37 4-Cl H ~ ~CH3 Po.l195 - 197 38 2,4-C1 H ~ ~C~ Po.l202 - 204 39 4-Br H 2 ~CH Po os199 - 201 402-Ci,4-Br H-CH-CH~CH3 Bp :- 207 - 208 10~4~73 Table 1: (continued) Ex R(n) Rl ~ b-p- (C~

41 - 4-CF3 H -CH2-CH~SH3b Po't 186 - 188 42 2,4_CI 3-~U~ -~ 2~ ~''05~ 204 - 206 II s A ~ -CH2-Example ~) 1(n1)R3 b.p./m.p,( ~) ,_, __ _ 43 4 Cl H -CH3 5 9 9 44 4_Br H ~ -CH3 0'01S 193 _ 194 4-C~3 ~ -CH3 b~P~o5s 175 - 177 46 2-Cl,4-~r H -CH3 b.p ; 205 - 20~
,D~
- 47 4-Cl H CH ~ CH b.~,1s 201 - 203 48 4-Br ~ CH~ CH3 b 4 49 4-CF3 ~2 CH3 b~Po~o~s 178 - 17~

S0 2,4~Cl H-OH2-CH\ 3 b,po,o5, 212 - 214 CH3 m.p- ~9 101 51 2-Cl,4-~r HCH~ 3 ~Po.1t 207 - 209 3 ~p. 94 - ~5 1094~73 , H2 c~ 3 III: A = -CH-}:xan~ple R(n) 1 (nl ~1 R3 b.p./m.p. (C) . . .. _. _ I ., ~__ 52 4-Cl ~ H -CH3 P ~ 05 ~ 186 - 187 ;3 4-Br ~1 -CH3 b ~;5 188 - 190 54 4-C~3 H CH3 0; 1 ~ 178 2, 4-Cl H -CH3 b ; 5 t 195 - 196 56 2-Cl, 4-Br H -CH3 P; 1 s 205 - 208 57 ¦ 4-Cl ~ CH2-CH\ 3 ¦ 0, I

58 4-Er H 2 3 0 ' 1 194 - 197 59 ~ 4-C 3 ¦ H ;-Cl~ 3 ~ 0; 5: 176 - 177 2, 4-Cl H -CH2-~ H3 P; 1: 197 ~ 198 61 Z-Cl, 4-B:r H CH2 CH3 oP; o5 204 - 205 . ~ . . .

16 -- _ 10~4 573 Table -: (R) ~ ~ -0-CH-C-0-Z

EXample(R)n Z b-P-,(C~
No.
_ .

62 4-Cl -CH2CH2C=N b.p.0~1 20Q - 203 63 2,4-Cl n b.p~~1 214 - 216 64 4-Br " b-p-o,o5: 207 - 210 652-C1,4-CF3 0,05: 190 192 66 4-Cl -CH(CH3)C_N 0'1 196 - 198 67 2,4-Cl n b.p. ~ ~ 1 200 ~ 202 fi8 4-Br ~ 0~05.~
69 4-CF3 n b.p. 0~l 184 - 186 702-Cl, 4-Br ~ b.p. 206 - 209 10~573 Exal[ ple( R) n ;~ m.p. ( C ) .. . _ _, .. , ._ . __ 71 4-Cl ~ OCH3 64-66 72 2, 4-Cl ~ C-OCH;~, 85-87 73 4-Cl -~-CO-CH2 -CH5 44-47 . 74 4-CF3 ~-Cl 91-92 2, 4-Cl ~-C-OCH2 -CH3 67-70 76 2, 4-Cl ~-C=C-C-OCH3 102-104 . 77 4-CF3 ~)-C-OCH3 67 69 78 2 ,4-~:1 _~ 101-103 ,Co~~CHS .

79 4- Cl --~C-OCH3 81-82 80 2, 4- Cl ~0 3 104-106 109~;73 ~Q ~CH--C--S--CH2~ R3 O
R(n) R~

~ample R(n)R1 (n1 ) R3 ~ C) _ 81 4-Cl ~ --C~I3 Bpo 2:220 -- 222 82 4--Cl ~ C~3 Bpo 05: 214 -- 216 83 4--Cl --C~2 C~ Bpo 05: 223 -- 224 84 2,4-Cl E[ ~CE13 13po.1: 234 -- 236 2, 4~Cl ~ C}13 ~P0 . 1 237 -- 239 86 ~CI?3 El c ~~3 Bpo. 2: 19~ -- 197 87 CF3 1~ _ ~P0 ~ Z~7 ~ 210 109~S73 Example 88 2-~4'-(2",4"-Dichlorobenzyl)-phenoxy~-propionyllactic acid methyl ester 44 grams of 2-L4'-(2",4"-dichlorobenzyl)-phenoxy~-propionic acid~ 27 grams of 2-bromopropionic acid methyl ester, 21 grams of anhydrous potassium carbonate and 100 ml of acetone were stirred at 60C for 8 hours. After cooling to 20C the inorganic salts were filtered off. The acetone was distilled off from the filtrate and the residue was distilled in vacuo.
51 grams (91.6% of the theoretical yield) of the follow-ing compound having a Bpo 05 : 165 - 166C were obtained.

Cl- ~ C 2 ~ -0-CH cl-o-$ -IC~-OCH3 Cl Example 89 2-14'(4"-Chlorophenoxy)-phenoxy] -propionyltar~ronic acid diethyl ester 32 grams of the sodium salt of 2-~4'-(4"-chlorophenoxy)-phenox~ -propionic acid, 27 g of bromomalonic acid diethyl ester, 1 ml of dimethylformamide and 150 ml of toluene were stirred at 80C for 18 hours. After filtering off the sodium bromide with suction, the toluene and the excess of bromo-malonic acid diethyl ester were distilled off from the filtrate.
43 grams of light yellow oil (96.0% of the theoretical 10~ ~573 yield) ~ere obtained. nD25 : 1.5300.

Cl- ~ -0- ~ -0-CH-IC-0-CH

Example 90 2-[4'-(2",4"-Dichlorophenoxy)-phenoxy~-propionyltartronic acid diethyl ester 35 g of the sodium salt of 2-[4'-(2",4"-dichlorophenoxy)-phenoxy~-propionic acid, 27 grams of bromomalonic acid diethyl ester, 1 ml of dimethylformamide and 150 ml of toluene were stirred at 80C for 18 hours. After cooling to 20C and fil-tering off the sodium bromide with suction, the toluene and the excess bromomalonic acid diethyl ester were distilled off from the filtrate.
47 grams of light yellow oil (97% of the theoreticalyield) were obtained. nD25 : I.5337.

Cl-~ ~ -0- ~ -0-CH-CI-0-CH
~ O COOC2H5 Cl Example 91 2-~4'-(2",4"-Dichlorophenoxy)-phenoxy~-propionylglycine methyl ester -At a temperature of 10C - 15C a solution of 24 grams 10~i~573 (O~076 mole) of 2-[4'-(2~,4~-dichlorophenoxy)-phenoxy]-propiunic acid chloride in 40 ml of tolu~ne were added drop-wise over a period of 30 minuteB to 14 grams (0.152 mole) of gl~cine ester, ~reshly relea~ed from glycine methyl ester chlorohydrate, dissolved in 80 ml of toluene. The mixture wa~ then ~tirred for 2 houra at 15 to 22C. The resulting glycine metbyl e~ter chlorohydrate Wa8 filtered off with 8UC-tion. The toluene wa8 distilled off in vacuo from the filtrate.
30 grams o~ light yellow oil, ~ 25 : 1.5652 w~re o~tained.

Cl ~ o ~ ~-~E~ CH2-C-OCH3 Cl 0 H 0 There ~hould also be mentioned 2-~'-t4N-chlorophenoxy~-phenoxy]-propionylthioglycolic ~cid methyl eYter.

BIOLOGICAL EX~MPLES
~BRBICIDES
In these Example~, result~ were determined by evaluation according to Bolle'~ ~cheme (NachrichteDblatt des Deutschen Pflanze~schutzdi2nstes 16, 1964, 92 - 94).

10'3~;73 Evaluation scheme Numerical Percentage damage to value Weeds Crops 2 97.5 to < 100 > 0 to 2.5 3 95to < 97.5 > 2.5 to 5 4 9Oto < 95 > 5 to 10 85to < 9O > 10 to 15 6 75to < 85 > 15 to 25 7 65to < 75 > 25 to 35 8 32.5 to < 65 > 35 to 67.5 9 0 to < 32.5 > 67.5 to 100 Example I: Pre-emergence treatment Seeds of various grasses were sown in pots and spray powders or emulsion concentra~es of a number of compounds of the invention were sprayed in different doses on to the soil surface. Fluorodifen and Mecoprop were used as comparison agents. The pots were then placed in a greenhouse for 4 weeks and the results determined by evaluation according to Bolle's scheme. The results are shown in Table A. As can be seen, the compounds according to the invention listed in Table A
exhibit a very good action against weed grasses. For most types of grass this is true even at very low dosages, for example 0.15 kg of active substance/ha. Fluorodifen and ; Mecoprop are substantially weaker in their action against grasses.

. , ~ .

lO~S73 Table A:
Weed evalu~tion number in the caee of pre-emergence tre~tment Compound Dosage Types of plant according t ~Cg/ha A S ~
to E:xample ALSA LO EC
2.5 2 2 3 0.6 3 3 5 2 2 2.5 3 1 1 t 0.6 4 2 1 2 8 2.5 3 1 1 2 0.6 3 2 2 3 2.5 0.6 1 3 - 1 2 11 2.5 2 0.6 2 2 12 2.5 0.6 2 2 2 13 2.5 2 0.6 4 2 26 2.5 2 0.6 2 2 37 2.5 0.6 3 2 3 3 38 2.5 - 1 1 1 0.6 - 3 3 4 41 2.5 0.6 . 3 43 2.5 2 ~1.6 3 2 1 2 44 2.5 0.6 1 2 47 2.5 2 0.6 4 2 2 3 53 2.5 0.6 . 1 2 54 2.5 0.6 2 .

~0~73 Con~ound Dosage Type~ of plant according ~ Kg/ha A S ) to Example AL SA LO E~

2.5 0.6 2 56 2.5 3 0.6 4 2 57 2.5 2 1 ~ 1 0.6 3 2 2 2 63 2.5 0.6 2 3 2 64 5 . 0 1.2 - -- 2 6~ 5.0 ~
1.2 -- -- 2 68 5.0 1 .2 72 2. 5 2 3 0.6 3 6 3 3 73 2.5 4 2 1 2 0.6 ~i 4 2 3 2.5 3 1 1 3 0.6 4 ~ 3 4 Fluorodifen 2. 5 7 t 1 4 0.6 8 5 8 8 0.15 8 7 8 9 2.5 4 3 5 3 M~oprop 0. 6 7 6 8 7 0.15 8 ~ 9 8 SA ~ Setari~ :
LO ~ Lolium EC - Echinc~clllo~
AS -- Ac!~ive ~ub~tarce ~n~73 Example II: Post-emergence treatment Seeds of various grasses were sown in pots and cultivated in the greenhouse. 3 weeks after sowing, a number of compounds of the invention were applied in different doses on to the plants in the form of spray powders or emulsion concentrates, and after standing for 4 weeks in the greenhouse the action of the compounds was evaluated according to Bolle's scheme. Fluorodifen and Mecoprop were used as a comparison.
As can be seen from the results listed in Table B, com-lo pounds of the invention exhibit a good to very good action against the weed grasses, and are superior to the known agents Fluorodifen and Mecoprop.
Example III: Post-emergence treatment Using the same method as in E~ample II (Post-emergence treatment), various crop plants were sprayed with suspensions or emulsions of compounds of the invention mentioned in Examples I and II. Even at a high dosage of 2.5kg/ha, soya beans, peanuts, dwarf beans, field beans,~peas, lucerne, flax, cabbage, rape, cucumber, sunflower, tobacco, carrots, celery and sugar beet showed no damage. Barley and wheat showed no reaction to the preparaticns according to E~amples 1, 2, 8, 11, 37, 38, 43, 47~ 53, 56 and 57.
Similar results were obtained when the compounds were sprayed on to the soil surface in the pre-emergence method.

109.~573 Table B:
Weed evaluation nunibera in the case of post-emergence treatment Compound Dosage ~pe~ of plant according ( Kg/ha A S ) to Exa~ple AL S.A LO

t 2.5 0.6 1 1 4 2 2.5 -- 1 t 0.6 -- 4 3 8 2.5 - 1 2 0.6 - 2 5 3 2.5 0.6 2 11 2,5 0.6 2 12 2.5 0.6 t 13 2.5 1 1 1 t 0.6 1 26 2.5 0.6 37 2,,5 3 2 - ~
0.6 4 4 -- 1 38 2.5 - 1 3 41 2. 5 0.6 1 1 2 43 2.5 1 1 4 1~.6 2 2 5 4~ 2.5 I ~ 1 1 0.6 47 2.5 - 1 2 2 0.6 - ~i 6 53 2.5 0.6 1 - 1 .
54 2.5 0.6 :
.

' 109'~ 73 Co~und Doaage Types of plant according ( ~g/ha A S ) to E:xan~ple AL SA LO I~C AV
. . .
2.5 0.6 56 2.5 -- t 0.6 -- 1 1 1 57 2.5 0,.6 4 63 2.5 1 1 4 64 2.5 - -- 3 0.6 -- - 6 67 2.5 1 1 - 1 0.6 1 3 - 1 68 2.5 - 4 0.6 5 6 2.5 t 0.6 2 1 2 2.. 5 8 2 6 4 8 Flllorodife~ 0.6 8 3 8 6 8 0.15 9 5 9 8 9 2.5 8 7 8 8 8 oprop 0. 6 9 8 9 9 9 0.15 9 9 9 9 9 AV -- ~el~a AL - ~ , 8A - Set~ria ~Ch~nochloe~

10~ 1~73 BIOLOGICAL EXAMPLES
~GICIDES
In these Examples, the following were used as comparison agents:
A = Combination of 5,6-diyhdro-2methyl-1,4~oxathiin-3-carboxanilide and methoxyethyl Hg silicate B = Manganese ethylene-1,2-bis-dithiOcarbamate D = Tetramethylthiuram-disulphide (TMTD) E = S-ethyl-N-(3-dimethylam nopropyl)-thiolcarbamate hydrochloride (Prothiocarb).
Example IV
Barley seeds infected with Ustilago nuda td1egree of infection 15%) were dressed with compounds according to the invention in the concentrations given in Table C. sown in pots, and cultivated first at a low temperature and later at higher temperatures (20C) in a greenhouse. The combination A was used as co~parison agent. 10-12 weeks later, the sound stems and the stems infected with Ustila~o nuda were counted, the degree of infection was determined in each case, and finally the degree of action calculated. The results are shown ir~ Table C.

~0'3 ~S73 Table C~

Compound ~ffect in % of 1 g o~ dressing agent according per 100 kg of ~eed to Example .
1 (50 % ~trength) 100 95 60 37 (50 % strength) - - - 100 80 89 (50 % strength) - - - 100 90 13 (50 % ~trengt~ 100 70 43 (50 % ~trength) - - - 100 70 ~ , . . . . .. .
73 (50 % strength) - 100 95 50 A ~50 % strength) 100 sa go untreated infected p'~ ' ' Table C ~hows the excellent action, ~uperior to that of the cGmpari~o~ agent ~, of compound~ o~ the i~vention ~gainst U~til~a~o nuda.
Example V:
Summer barley ~eed~ naturally infected with Helmintho-~vorium arami eum, with a degree o~ infeation of 24 X, were dre~sed in various concentration~ with 50 % dre~sing agent~
containing the agent~ ~hGwn in Table D. The seeds were sown in trays which were ~ubseguently placed in a greenhouse. Later, ~09~73 both the plant~ infected with He ~intho-cDorium r ~ neum and those that were 20und were counted, the degree of infection in each case Wa8 determined, and finally the degree of action w~ calculated. The result are given in Table D.

Table D:

Dre~sinq agent . Effect in ~ of 1 g of dreQsing age~t according to per 100 kg of seed Example . 300 250 200 100 __ _ . . . ___ 67 (50 % ~trength) _ _ 100 80 .. .. . _ . .
a (50 % ~trength) _ 100 95 ~ _ . ~_ ..
B (80 % ~trength) 75 _ 60 --_ ~ _ u~treated infected .
plant~ 0 ,~ , .

. . . _ ~he ~ 8 in T~ble ~ shGw t~e excellent actio~ of the compound o~ th~ $nvention agai~t H2lmintho~0rium Dnd the ~periority oE thi~ mercury-free ~ompo~nd over the me~cury-free compari~on agent B and ~he ~ercury-containi~g c ~ riJo~
agent A.
ExamDle VI-.
Sugar beet ~ed~ naturally infected with Phoma betae uith a degree of infection of approximat~ly 60 %~ ~ere dreA~ed with the compound o~ the in~ention shGwn in Table E and ~i~h co~p~rison agent D, pla~ in tray~ ~nd cultivated ~t 20C i~

greenhou~. 3 wOEek~ ~ter sowing, the ~ug~r beet plant~

10~t~S73 were examined for infection with Phoma betae and the degree of action of the compound of the invention was determined.

The results are shown in Table E.

Table E:

Dressing agent Effect in % of 1 g of active according to substance per 100 kg of seed Example -56 (50% strength) - - 100 80 D (80% strength) 100 95 85 75 untreated infected 0 plants Example VII:
The compound shown in Table F was uniformly dis~ributed and mixed into a soil uniformly but heavily infected with Pythium ultimum. The soil treated in this manner was intro-duced into plastic po~s and 10 pea seeds were then sown in each pot. The procedure was repeated with agent E for com-parison. 8 to 10 days after sowing, the evaluation of the experiments was carried out by determining the number of sound plants that had emerged and calculating the degree of action of the compound of the invention. The controls used were pots containing infected, untreated earth.

10!? ~;73 Ta~le F-Compound Effect irl % of 1 mg of active according ~ubstance per kg of soil to Example , . . ~

~treated infect:ed plantQ o Table~ nd F show the excelle~t ~lmgicidal action of t}le co~pound~s, whic~h i~ sup~rior to t~at of the ca~pari~on age~ts D ~nd E. - -

Claims

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

1. A compound of the general formula (I) in which n represents an integer from 1 to 3, n1 represents an integer from 0 to 3, and n and n1 may be the same or different, R represents a halogen atom, CF3, (C1-C4)-alkyl, or nitro, R1 represents hydrogen, a halogen atom or (C1-C4)-alkyl, and any two or more of the R
and R1 moieties may be the same or different, X represents -0- or -CH2-, Y represents -0-, -S- or -NH- and Z represents a cyanoethyl group or a radical of the general formula , in which A represents a methylene group which may be unsubstituted or substituted by -CH3, -C2H5, -COCH3 or by another radical of the general formula -COOR'3, or a phenylene or styryl radical, which radicals may be unsubstituted or substituted in the ring by one or two of the same or different substituents selected from halogen atoms and (C1-C4)-alkyl and nitro groups, and R3 and R'3 which may be the same or different, each represents a (C1-C4)-alkyl group.

2. A compound as claimed in claim 1, in which n = 1 or 2.

3. A compound as claimed in claim 2, in which R(n) represents 4-C1, 2,4-C1, 4-Br, 2-C1, 4-Br, or 4-CF3.

4. A compound as claimed in claim 1 in which n1 = 0.

5. A compound as claimed in claim 1 in which Y represents an oxygen atom.

6. A compound as claimed in claim 1 in which X represents an oxygen atom.

7. A compound as claimed in claim 1 in which Z represents a cyanoethyl group or a radical of the general formula -A-COOR3 in which A = -CH2-, -CH(CH3)- or -CH(C2H5)- and R3 represents a methyl or ethyl group.

8. A compound as claimed in claim 1, which has the formula

9. A compound as claimed in claim 1, which has the formula

10. A compound as clamed in claim 1, which has the formula

11. A compound as claimed in claim 1, which has the formula

12. A compound as claimed in claim 1, which has the formula

13. A compound as claimed in claim 1, which has the formula

14 . A compound as claimed in claim 1, which has the formula

15. A compound as claimed in claim 1, which has the formula

16. A compound as claimed in claim 1, which has the formula

17. A compound as claimed in claim 1, which has the formula

18. A compound as claimed in claim 1, which has the formula

19. A compound as claimed in claim 1, which has the formula

20. A process for the preparation of a compound claimed in claim 1, which comprises reacting (a) a compound of the general formula (II) in which n, n1, R, R1, X and Y have the meanings given in claim 1, or an alkali metal or ammonium salt thereof with a compound of the general formula Hal - Z (III) in which Z has the meaning given in claim 1 and Hal represents a halogen atom, or (b) a compound of the general formula (IV) in which n, n1, R, R1, and X have the meanings given in claim 1 and Hal has the meaning given above, with a compound of the general formula HYZ (V) in which Y and Z have the meanings given in claim 1, or an alkali metal or ammonium salt thereof.

21. A method of combating weed grasses, which comprises applying to the weed grass or to an area or soil infested with, or liable to infestation by, a weed grass, a compound as claimed in claim 1.

22. A method as claimed in claim 21 for combating weed grasses in crop plants, which comprises applying the compound or preparation to the weed grass or to the crop area or soil.

23. A method as claimled in claim 21 or claim 22, wherein the weed grass is Avena, Alopecurus, Lolium, Setaria, Echinocloa or Digitaria.

24. A method of conbating fungal infections, which comprises applying to the fungus or to an object, material or area infected with, or liable to infection with, a fungus, a compound as claimed in claim 1.

25. A method as claimed in claim 24 for combating fungal infections in crop plants, which comprises applying the compound or preparation to the fungus or to the crop, crop area, seed or soil.

26. A method as claimed in claim 24 or claim 25, wherein the fungus is Piricularia oryzae, rust fungus, Botrytis cinerea, Plasmopara viticola, Phytophthora infestans, a true type of mildew, Rhizoctonia solani, Septoria nodorum, Ustilago nuda, Phorna betaw, Pythium ultimum or Helminthosporium gramineum.

27. A method as claimed in claim 22 or claim 25 wherein the crop is soya beans, peanuts, dwarf beans, field beans, peas, lucerne, flax, cabbage, rape, cucumber, sunflower, tobacco, carrots, celery or sugar beet.

28. A method as claimed in claim 22 or claim 25 wherein the crop is a cereal.

29. A method as claimed in claim 21 or claim 24 wherein the compound is applied in an amount of from 0.1 to 10 kg/ha.

30. A method as claimed in claim 21 or claim 24 wherein the compound is applied in an amount of from 0.1 to 3 kg/ha.