CA1090367A - Phenoxyphenoxyalkanecarboxylic acid derivatives having a herbicidal and plant growth regulating action - Google Patents
Phenoxyphenoxyalkanecarboxylic acid derivatives having a herbicidal and plant growth regulating actionInfo
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- CA1090367A CA1090367A CA306,425A CA306425A CA1090367A CA 1090367 A CA1090367 A CA 1090367A CA 306425 A CA306425 A CA 306425A CA 1090367 A CA1090367 A CA 1090367A
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-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
- C07C205/39—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by esterified hydroxy groups
- C07C205/42—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by esterified hydroxy groups having nitro groups or esterified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
- C07C205/43—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by esterified hydroxy groups having nitro groups or esterified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton to carbon atoms of the same non-condensed six-membered aromatic ring or to carbon atoms of six-membered aromatic rings being part of the same condensed ring system
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N39/00—Biocides, pest repellants or attractants, or plant growth regulators containing aryloxy- or arylthio-aliphatic or cycloaliphatic compounds, containing the group or, e.g. phenoxyethylamine, phenylthio-acetonitrile, phenoxyacetone
- A01N39/02—Aryloxy-carboxylic acids; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
- C07C205/27—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by etherified hydroxy groups
- C07C205/35—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by etherified hydroxy groups having nitro groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
- C07C205/36—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by etherified hydroxy groups having nitro groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton to carbon atoms of the same non-condensed six-membered aromatic ring or to carbon atoms of six-membered aromatic rings being part of the same condensed ring system
- C07C205/38—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by etherified hydroxy groups having nitro groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton to carbon atoms of the same non-condensed six-membered aromatic ring or to carbon atoms of six-membered aromatic rings being part of the same condensed ring system the oxygen atom of at least one of the etherified hydroxy groups being further bound to a carbon atom of a six-membered aromatic ring, e.g. nitrodiphenyl ethers
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C327/00—Thiocarboxylic acids
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Agronomy & Crop Science (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
Abstract of the Disclosure Phenoxyphenoxyalkanecarboxylic acid derivatives with herbicidal and plant-growth regulating, especially plant growth inhibiting, action are disclosed.
These compounds have the formula
These compounds have the formula
Description
0 90 3 ~ ~
The present invention relates to novel phenoxyphenoxy-alkanecarboxylic acid derivatives having a herbicidal and plant growth regulating action, processes for their production, compositions which contain these derivatives as active ingredient and to a method of controlling or regulating undesirable plant growth which comprises the use of the novel c~lpounds.
The phenoxyphenoxyalkanecarboxylic acid derivatives of the invention have the formula I
N02 O-~-A
4 ~ _0 ~ R2 (I) wherein Rl represents hydrogen, Cl-C4alkyl or C2-C8alkoxyalkyl, R2 represents hydrogen or Cl-C4alkyl, R3 represents halogen, cyano or nitro, R4 represents halogen, cyano or trifluoromethyl, A represents cyano or the group -COB, B represents a radical OR5, SR6 or NR7R8, R5 represents hydrogen or the cation of a base n M n ~, wherein M represents an alkali metal or alkaline earth metal cation or an ammonio radical .
... ... . . ..... ........... . ....... .... . .. . . .. .. .. . .. .
~~' 10 ~0 3~7 R - N R
R R
b c n as integer 1, 2 or 3 corresponds to the ~alency of the cation, whilst Ra, Rb, Rc and Rd, each independently of the other, represent hydrogen, benzyl or an alkyl radical which is unsubstituted or substituted by -OH, -NH2 or Cl-C4alkoxy; and R5 further represents -a Cl-C8alkyl radical which is unsubstituted or substituted by halogen, cyano, nitro, hydroxyl or a 5- to 6-membered nitrogen- containing --- heterocyclic ring system, and a C2-C8alkyl radical which can be interrupted by oxygen, ~
sulphur, nitrogen, carbonyl or carbonyloxy, .
-a C3-C6cycloalkyl radical, -a C3-C6alkenyl or alkynyl radical which can be substituted by halogen, -a phenyl or benzyl radical which can be substituted by halogen, cyano, nitro, Cl-C4alkyl, Cl-C4alkoxy or trifluor~methyl, R6 represents a Cl-C8alkyl radical which can be substituted by halogen, cyano, nitro or hydroxyl or interrupted by oxygen, sulphur, nitrogen, carbonyl or carbonyloxy, a C3-C6cycloalkyl radical, a C3-C6alkenyl or alkynyl radical which can be substituted by halogen, a phenyl or benzyl radical which can be substituted by halogen, cyano, nitro, Cl-C4alkyl, Cl-C4alkoxy or trifluoromethyl, R7 represents hydrogen, a Cl-C8alkyl radical which can - . -- - .. . . ~ ~ - ~ .
, - ~. ~ . . .
- ::
10903~
_ 3 _ be substituted by halogen, cyano or hydroxyl, and a C2-C8alkyl radical which can be interrupted by oxygen, R8 represents a Cl-C4alkyl radical or a C3-C4alkyl radical, and R7 and R8, together with the nitrogen atom to which they are attached, also represent a 5- to 6-membered heterocyclic radical which can be interrupted by oxygen, sulphur, an imino, Cl-C4alkylimino or phenyl-imino group. ~ -In the above formula, the alkyl radicals are both branched and unbranched and contain the indicated number of carbon atoms. The symbols R7 and R8 preferably re-present hydrogen or lower alkyl groups. Individual alkyl groups however can also be unsaturated or aromatic (phenyl) or araliphatic (benzyl) and both together with the nitrogen atom to which they are attached can form a 5- to 6-membered heterocyclic ring system.
Herbicidal active c~mpounds based on substituted di-phenyl ethers are known, for example from Swiss patent specification 424,326. Recently, herbicidally active phenoxyphenoxyalkanecarboxylic acids have been described, in which connection attention is drawn for example to German Offenlegungsschrift 2,433,067.
The present invention provides a novel group of phenoxy-phenoxyalkanecarboxylic acid derivatives which, in low rates of application, are able to influence the growth of plants in a manner which is agriculturally advantageous.
The novel active compounds of the formula I of the present invention possess a general herbicidal action which is non-specific to grasses, especially on post-emergent application, and they can be used as weed kill~rs in `` 10 90 36 7 crops of mono- and dicotyledonous plants.
The active compounds also possess an advantageous growth-regulating action (growth inhibition).
In particular, they inhibit the growth of dicotyledonous plants. Exemplary of the useful applica~ion of the compounds of the present invention are:
- the reduction of the vegetative growth in soya and similar leguminosae, resulting in an increase in the yield of these plants;
- the inhibition of the undesirable growth of suckers in tobacco plants, the leading shoots of which have been cut, thus promoting the fonllation of larger and finer leavesi - the inhibition of the growth of grass and dicotyledonous ~ plants, such as fruit trees, ornamental trees, bushes ~nd hedgerows, with the object of saving cutting work.
The compounds of the present invention have a low toxicity to warm-blooded animals and their application causes no problems. The rate of application is between 0.1 and 5 kg per hectare.
The novel compounds of the formula I are obtained by reactions of chemical synthesis which are known per se, for example in accordance with the following reaction scheme:
. ' ..
: .
: :
-. ~
: . : . : : :
- : "~
- 1()903t~7 _ 5 _ NO2 ~1 NO2 OH
R4 ~ ~1 + HO ~ __,~R~ ~ O _ ~ C12 1 ~3 NO2 OH ~ 2 ~
4~ ~ O ~ Cl R4 ~ ~ -~2 Rl Hal - C - A
~ Rl / Rl R ~ ~ 2 R ~ ~ 202 In the above formulae, Hal is a halogen atom, preferably a chlorine or bromine atom, and A, Rl, R2 and R4 are as defined in formula I.
Ortho-nitrochlorobenzene substituted in the para-position -by the radical R4 is reacted with resorcinol at elevated temperature in the presence of an acid acceptor. There should be a slight excess of resorcinol over the chloro-benzene. When the reaction is complete, the reaction mass is poured into water and the resulting diphenyl ether is extracted from the aqueous suspension with a solvent which is not miscible with water. A trace of copper powder can be added to hasten 10903ti7 the condensation. The condensation is advantageously carried out in an oil bath at about 200C. Attention is drawn to the following literature: Weygand Hilgetag, "Organisch-Chemische Experimentierkunst, 3rd edition 1964, 435, US patent specification 3,080,225, German Offenlegungsschrift 2,433,066, and German Auslege-schrift 1,187,852.
A nitro group can be introduced into the still free para-position of the diphenyl ether by nitration in glacial acetic acid, ethylene chloride or sulphuric acid. A
chlorine at~m can be introduced into this position by treatment with chlorine in glacial acetic acid. If R3 is cyano or bromine, the chlorine atom is replaced in this stage for example by reaction with KCN (see Adv. Chem.
Ser. 132 (1974), 252, or J. Organomet. Chem. 54 (1973)C
57) or KBr or NaBr, or the aniline obtained by reduction of the N02 group is subjected to a Sandmeyer reaction.
The process of the invention for the production of phenoxyphenoxyalkanecarboxylic acid derivatives of the ormula I c~mprises reacting, in a manner known per se, a diphenyl ether of the formula II
N02 OX . .
R ~ ~ (II) wherein X represents hydrogen or the cation of an alkali metal or alkaline earth metal, and R3 and R4 are as defined in formula I, with an ~-halogenocarboxylic acid derivative of the formula III
Hal - Cl_ A (III) wherein A, Rl and R2 are as defined in formula I, and : . ~, ~ ' . ,' .
, . :
- . . , - . :
~. ~
lV903~;7 Hal represents a halogen atom, preferably a chlorine or bromine atom.
The reactants of the formulae II and III are used in about stoichiometric amounts. The reaction is carried out advantageously in the presence of an organic solvent which is inert to the reactants, at a temperature between room temperature and the boiling temperature of the reaction mixture, if appropriate, i.e. if X is hydrogen, in the presence of an acid acceptor.
When the reaction is complete, which can take from 1 to 8 hours, the reaction product is isolated, for example by ;
distilling off the solvent and pouring the residue into ice-water.
Suitable solvents for this reaction are in particular organic aprotic solvents which dissolve the reactants but do not react with them. The condensation agents are inorganic bases, such as NaOH, KOH, NaOCH3 etc., but also organic bases, such as tertiary amines.
The following Examples illustrate methods of manufacturing a number of active compounds of the formula I. Further active compounds obtained in corresponding manner are listed in the following table.
These phenoxyphenoxyalkanecarboxylic acid derivatives of the formula I are stable compounds which are soluble in -conventional organic solvents, such as alcohols, ethers, ketones, dimethyl formamide, dimethyl sulphoxide etc.
10903~7 Example 1 34,1 g (0,1 mole) of 2-nitro-4-trifluoromethyl-3'-acetoxy-diphenyl ether are dissolved in 200 ml of acetic acid and equimolar amounts of chlorine are introduced into the solution at 40C with good stirring. The reaction course is followed by gas chromatography. When the reaction is complete, the resulting solution is poured into ice-water and extracted with toluene/ethyl acetate (1:1). The organic solvent is distilled off, giving an oil which is sapnnified with 30% methanolic sodium hydroxide solution to give the free phenol, The resulting oil has a boiling point of 159-165C at 0.03 mm Hg.
Yield: 23,5 g, 23.5 g of 2-nitro-4-trifluoromethyl-3'-hydroxy-4'-chloro-diphenyl ether are dissolved in 30 ml of ethyl methyl ketone, To this solution are added 18 ml of methyl 2-bromopropionate, 18 g of potassium carbonate and a trace of potassium bromide on the tip of a spatula, The reaction mixture is stirred overnight at a bath temperature of 80C, Insoluble constituents are removed by filtration and the solvent is distilled off, The residual oil is distilled in a high vacuum. Boiling point: 172C/
0,015 mm Hg, Yield: 20,8 g, CH
F3C ~ o _ ~ Cl ' : ' ~ ,-~' ' '; .... ':
-.
, . ': ', ' '' 1(1903~7 g Example 2 a) 68.2 g of 2-nitro-4-trimethyl-3'-acetoxy-diphenyl ether are dissolved in 80 ml of ethylene chloride and nitrating acid (1:1) is added dropwise at 0-5C. When the addition is complete, the reaction mixture is stirred for a further 1/2 hour and the reaction product is poured into water. The precipitated product is extracted with ethyl acetate/toluene (1:1). The solvent is distilled off, affording a solid product which is recrystallised from alcohol/water. Melting point: 129~-130C. Yield:
47 4 g (61.4% of theory).
b) 200 ml of methanol are added to 47.4 g of 2,4'-dinitro-4-trifluoromethyl-3'-acetoxy-diphenyl ether and, after addition of the equimolar amount of methanolic KOH, the reaction mixture is allowed to stand for half an hour.
The solvent is distilled off and the residue is dissolved in water. After acidification with 2N HCl, the precipitated phenol is extracted with ethyl acetate/
toluene (1:1). The solvent is dis~illed off, affording 44.5 g of an oil which crystallises on standing. Melting point: 78-79C.
c) 17.2 g of 2,4'-dinitro-4-trifluoromethyl-3'-hydroxy-diphenyl ether are dissolved in 50 ml of 2-butanone and, after addition of 13.4 g of methyl 2-bromopropionate, 13.8 g of potassium carbonate and a trace of potassium iodide on the tip of a spatula, the reaction mixture is stirred overnight at a bath temperature of 80C. The reaction mixture is subsequently filtered and the filtrate is concentrated. The residual oil is distilled in a high vacu~tm. Boiling point: 217C/0.05 torr. Yield:
6.2 g of the compound of the formula 1(J903t~7 F3C ~ ~ N02 R
R4 ~ o ~ R3 - . _ .. . _ _ _ _ Rl R2 R3 R4 A . Physical constant (~C) . .. _ _ .. . I
CH3 H Cl CF3 COOCH3 b.p.:~72/0.015 CH3 H Cl Cl COOCH3 oil CH3 H N02 CF3 COOCH3 b.p.:217/0.05 CH3 H Br CF3 COOCH3 CH3 H Br Cl COOCH3 CH3 H N02 Cl COOCH3 m.p. 87-88 CH3 H N02 CF3 Cooc~l2cH=cH2 CH3 H N02 Cl COSCH3 CH3 H Cl Cl COOC2H4N(C2H5 2 CH3 H Cl CF3 CN
CH3 H Cl CF3 Cooc2H4ocH3 b.p. 200/0~001 CH3 H N02 CF3 (C2H5)2 CH3 H Cl CF3 COOCH3 ~H3 H Cl CF3 COOH m;p. 168-170 CH3 H Cl Cl COOH m.p. 125 CH3 H N02 CF3 COOH r~
CH3 H Cl CF3 00~ Na ~b _ _ :. : .
. . . .
.: ', . .- ~ ' ~
. .
. . . . . . . .
. . . . . . .. .
90 3 ~ 7 . . .. . . .
Rl R2 R3 ~4 A Phys cal ._ . . __ _ . .
CH3 H Cl CN COOCH3 oil CH3 H N02 CN COOCH3 b.p. 188/0.35 CH3 H Cl CF3 CoocH2cH=cH2 b.p. 200-230/
CH3 H Cl CF3 COSCH2CH=CH2 0.001 CH3 H Cl Cl COOC2H5 nD5 1.5705 CH3 H Cl Cl . n25 1.5596 CH3 H Cl Cl COOiC4Hg nD5 1.5604 H H N02 CF3 COOCH3 m.p. 107-108 H H N02 CF3 COOH m,p, 98-104 C2H5 HCl CF3 COOCH3 CH3 H Br CF3 COOCH3 CH3 CH3 Cl CF3 COOC2H5 CH3 H Cl CF3 ; COSCH3 oil CH3 H Cl CF3 COOCH2 ~ .p,:235/O,OOl CH3 H Cl CF3 COOiC4Hg oil CH3 H Cl CF3 COOCH2CH2Cl oil CH3 H Cl CF3 COO-sec.C4Hg .p.:200/O,OOl CH3 H Cl CF3 COOn-C3H7 .p.:190/O,OOl CH3 H Cl CF3 COOCH2C_CH oil CH3 H Cl CF3 CoocH2cHc2H5 .p.:200/O,OOl CH3cH
CH3 H Cl CF3 COON=C ~ 3 oil . CH3 CH3 H Cl CF3 COO ~ oil CH3 H Cl CF3 CH3 oil ", ~ .
. . ~ .
.
Rl R2 R3 R4 A Physical , _ _ __ , , ,_, _ constant ( C) CH3 H Cl CF3 COOCH2CH2N~ .
CH3 H Cl CF3 2CH2cH3 CH3 H Cl CF3 CONH .
CH3 H Cl CF3 CO ~ . .
CH3 H Cl CF3 CO- ~ . .
CH3 H Cl CF3 CoocH2cH3 .
CH3 H Cl CF3 CONOCH~ oil CH3 H Cl CF3 COS ~ b.p.:230/O.OOl CH3 ~ Cl CF3 COO ~ il CH3 H Cl CF3 _ _ ~ .
.. . ...... .. ..
, ~ . - - -.. ~.. ... ~ . :
.' ' .
.. . ...
~ , . ' .
The invention also relates to herbicidal and plant growth-regulating compositions which contain a novel active compound of the formula I, as well as to methods of controlling weeds by pre- and post-emergent application and of inhibiting the growth of mono- and dicotyledonous plants, especially grasses, cereals, soya and tobacco shoots.
The compositions of the present invention can be in the conventional formulations.
The compositions of the present invention are ob-tained in known n~anner by homogeneously mixing and grinding active substances of the general formula I with suitable carriers, with or wi~hout the addition of dispersants or æolvents which are ine~-t to the active substances. The active substances can be processed to the following formulations:
solid formulations: -dusts, tracking powders, granules (coated granules, impregnated granules and homogeneous granules);
active subs~ance concentrates which are dispersible in water:
wettable powders, pastes, emulsions;
liquid formulations: solutions.
The concentration of active substance in the above described compositions is between 0.1 and 95%, preferably between 1 and 80%. Formulations can be diluted to c~ncentrations as low as 0.001%. The rates of application are ordinarily from 0.1 to 10 kg, preferably from 0.25 to 5 kg, of active substance per hectare. The active compounds of the formula I can be formulated for e~ample as follows (parts are by weight):
- 109(~ '7 Dusts: The following subs~ance are used to prepare a) 5% and b) 2% dust:
a) 5 parts of 2-chloro-5-~2'-nitro-4'-tri-fluoromethyl-phenoxy)--phenoxy-propionic acid methyl ester, parts of talci b) 2 parts of active substance ' 1 part of highly dispersed silicic acid 97 parts of talc.
The active substances are mixed with the carriers and ground.
Granulate: The following,su~stances are used to prepare a 5% granulate:
parts of the above active substance 0.25 part of epichlorohydrin -0.25 part of cetyl polyglycol ether 3.25 parts of polyethylene glycol ~ 1 parts of kaolin (particle size 0.3-0.8 mm).
,The active substance is mixed with epichlorohydrin and the mixture is dissolved in 6 parts of acetone. Then poly-ethylene glycol and cetyl polyglycol ether are added. The resulting solution is sprayed on kaolin and subsequently evaporated in vacuo.
Wettable Po~ders .
The following constituents are used for prepare a) a 50%, b) a 25% and c) a 10% wettable powder: -a) 50 parts of 2-chloro-5-(2'-nitro-4'-trifluoro-methyl-phenoxy)-a-phenoxy-propionic acid methyl ester, parts of sodium dibutylnaphthylsulphonate.
3 parts of naphthalenesulphonic acid/phenolsul-phonic acid/formaldehyde condensate (3:2:1), parts of kaolin, 22 parts of Champagne chalk;
.: ~ :, . . ......................... . -- - -.
1~90;~t~7 - b) 2~ parts of the above active substance, parts of sodium oleylmethyltauride, ; 2.5 parts of naphthalenesulphonic acid/formaldehyde condensate, 0.5 part of carboxymethyl cellulose, parts of neutral potassium aluminium silicate, 62 parts of kaolin;
c) 10 parts of the above active substance, 3 parts of a mix~ure of the sodium salts of saturated fatty alcohol sulphates, parts of naphthalenesulphonic acid/formaldehyde condensate.
82 parts of kaolin.
The indicated active substance is applied to the - corresponding carriers (kaolin and chalk) and then these are mixed and ground, to yield wettable powders of e~cellent wettability and suspension power. By diluting these we~table powders with water it is possible to obtain suspensions of the desired concentration of active substance. Such suspensions are used for controlling weeds and grass-like weeds in crops of cultivated plants by the preemergent method and for treating areas of grass.
~, ' 0 90 3 ~ 7 _ 16 -Paste . _ The following substances are used to manufacture a 45% paste: -parts of 2_chloro-5-(2'-nitro-4'-trifluoro-methyl phenox~)--phen~xy-propionic acid methyl ester, S parts of sodium aluminium silicate, 14 parts o cetyl polyglycol ether with 8 moles of the ethylene oxide, 1 part of oleyl polyglycol ether with 5 moles of the ethylene oxide,
The present invention relates to novel phenoxyphenoxy-alkanecarboxylic acid derivatives having a herbicidal and plant growth regulating action, processes for their production, compositions which contain these derivatives as active ingredient and to a method of controlling or regulating undesirable plant growth which comprises the use of the novel c~lpounds.
The phenoxyphenoxyalkanecarboxylic acid derivatives of the invention have the formula I
N02 O-~-A
4 ~ _0 ~ R2 (I) wherein Rl represents hydrogen, Cl-C4alkyl or C2-C8alkoxyalkyl, R2 represents hydrogen or Cl-C4alkyl, R3 represents halogen, cyano or nitro, R4 represents halogen, cyano or trifluoromethyl, A represents cyano or the group -COB, B represents a radical OR5, SR6 or NR7R8, R5 represents hydrogen or the cation of a base n M n ~, wherein M represents an alkali metal or alkaline earth metal cation or an ammonio radical .
... ... . . ..... ........... . ....... .... . .. . . .. .. .. . .. .
~~' 10 ~0 3~7 R - N R
R R
b c n as integer 1, 2 or 3 corresponds to the ~alency of the cation, whilst Ra, Rb, Rc and Rd, each independently of the other, represent hydrogen, benzyl or an alkyl radical which is unsubstituted or substituted by -OH, -NH2 or Cl-C4alkoxy; and R5 further represents -a Cl-C8alkyl radical which is unsubstituted or substituted by halogen, cyano, nitro, hydroxyl or a 5- to 6-membered nitrogen- containing --- heterocyclic ring system, and a C2-C8alkyl radical which can be interrupted by oxygen, ~
sulphur, nitrogen, carbonyl or carbonyloxy, .
-a C3-C6cycloalkyl radical, -a C3-C6alkenyl or alkynyl radical which can be substituted by halogen, -a phenyl or benzyl radical which can be substituted by halogen, cyano, nitro, Cl-C4alkyl, Cl-C4alkoxy or trifluor~methyl, R6 represents a Cl-C8alkyl radical which can be substituted by halogen, cyano, nitro or hydroxyl or interrupted by oxygen, sulphur, nitrogen, carbonyl or carbonyloxy, a C3-C6cycloalkyl radical, a C3-C6alkenyl or alkynyl radical which can be substituted by halogen, a phenyl or benzyl radical which can be substituted by halogen, cyano, nitro, Cl-C4alkyl, Cl-C4alkoxy or trifluoromethyl, R7 represents hydrogen, a Cl-C8alkyl radical which can - . -- - .. . . ~ ~ - ~ .
, - ~. ~ . . .
- ::
10903~
_ 3 _ be substituted by halogen, cyano or hydroxyl, and a C2-C8alkyl radical which can be interrupted by oxygen, R8 represents a Cl-C4alkyl radical or a C3-C4alkyl radical, and R7 and R8, together with the nitrogen atom to which they are attached, also represent a 5- to 6-membered heterocyclic radical which can be interrupted by oxygen, sulphur, an imino, Cl-C4alkylimino or phenyl-imino group. ~ -In the above formula, the alkyl radicals are both branched and unbranched and contain the indicated number of carbon atoms. The symbols R7 and R8 preferably re-present hydrogen or lower alkyl groups. Individual alkyl groups however can also be unsaturated or aromatic (phenyl) or araliphatic (benzyl) and both together with the nitrogen atom to which they are attached can form a 5- to 6-membered heterocyclic ring system.
Herbicidal active c~mpounds based on substituted di-phenyl ethers are known, for example from Swiss patent specification 424,326. Recently, herbicidally active phenoxyphenoxyalkanecarboxylic acids have been described, in which connection attention is drawn for example to German Offenlegungsschrift 2,433,067.
The present invention provides a novel group of phenoxy-phenoxyalkanecarboxylic acid derivatives which, in low rates of application, are able to influence the growth of plants in a manner which is agriculturally advantageous.
The novel active compounds of the formula I of the present invention possess a general herbicidal action which is non-specific to grasses, especially on post-emergent application, and they can be used as weed kill~rs in `` 10 90 36 7 crops of mono- and dicotyledonous plants.
The active compounds also possess an advantageous growth-regulating action (growth inhibition).
In particular, they inhibit the growth of dicotyledonous plants. Exemplary of the useful applica~ion of the compounds of the present invention are:
- the reduction of the vegetative growth in soya and similar leguminosae, resulting in an increase in the yield of these plants;
- the inhibition of the undesirable growth of suckers in tobacco plants, the leading shoots of which have been cut, thus promoting the fonllation of larger and finer leavesi - the inhibition of the growth of grass and dicotyledonous ~ plants, such as fruit trees, ornamental trees, bushes ~nd hedgerows, with the object of saving cutting work.
The compounds of the present invention have a low toxicity to warm-blooded animals and their application causes no problems. The rate of application is between 0.1 and 5 kg per hectare.
The novel compounds of the formula I are obtained by reactions of chemical synthesis which are known per se, for example in accordance with the following reaction scheme:
. ' ..
: .
: :
-. ~
: . : . : : :
- : "~
- 1()903t~7 _ 5 _ NO2 ~1 NO2 OH
R4 ~ ~1 + HO ~ __,~R~ ~ O _ ~ C12 1 ~3 NO2 OH ~ 2 ~
4~ ~ O ~ Cl R4 ~ ~ -~2 Rl Hal - C - A
~ Rl / Rl R ~ ~ 2 R ~ ~ 202 In the above formulae, Hal is a halogen atom, preferably a chlorine or bromine atom, and A, Rl, R2 and R4 are as defined in formula I.
Ortho-nitrochlorobenzene substituted in the para-position -by the radical R4 is reacted with resorcinol at elevated temperature in the presence of an acid acceptor. There should be a slight excess of resorcinol over the chloro-benzene. When the reaction is complete, the reaction mass is poured into water and the resulting diphenyl ether is extracted from the aqueous suspension with a solvent which is not miscible with water. A trace of copper powder can be added to hasten 10903ti7 the condensation. The condensation is advantageously carried out in an oil bath at about 200C. Attention is drawn to the following literature: Weygand Hilgetag, "Organisch-Chemische Experimentierkunst, 3rd edition 1964, 435, US patent specification 3,080,225, German Offenlegungsschrift 2,433,066, and German Auslege-schrift 1,187,852.
A nitro group can be introduced into the still free para-position of the diphenyl ether by nitration in glacial acetic acid, ethylene chloride or sulphuric acid. A
chlorine at~m can be introduced into this position by treatment with chlorine in glacial acetic acid. If R3 is cyano or bromine, the chlorine atom is replaced in this stage for example by reaction with KCN (see Adv. Chem.
Ser. 132 (1974), 252, or J. Organomet. Chem. 54 (1973)C
57) or KBr or NaBr, or the aniline obtained by reduction of the N02 group is subjected to a Sandmeyer reaction.
The process of the invention for the production of phenoxyphenoxyalkanecarboxylic acid derivatives of the ormula I c~mprises reacting, in a manner known per se, a diphenyl ether of the formula II
N02 OX . .
R ~ ~ (II) wherein X represents hydrogen or the cation of an alkali metal or alkaline earth metal, and R3 and R4 are as defined in formula I, with an ~-halogenocarboxylic acid derivative of the formula III
Hal - Cl_ A (III) wherein A, Rl and R2 are as defined in formula I, and : . ~, ~ ' . ,' .
, . :
- . . , - . :
~. ~
lV903~;7 Hal represents a halogen atom, preferably a chlorine or bromine atom.
The reactants of the formulae II and III are used in about stoichiometric amounts. The reaction is carried out advantageously in the presence of an organic solvent which is inert to the reactants, at a temperature between room temperature and the boiling temperature of the reaction mixture, if appropriate, i.e. if X is hydrogen, in the presence of an acid acceptor.
When the reaction is complete, which can take from 1 to 8 hours, the reaction product is isolated, for example by ;
distilling off the solvent and pouring the residue into ice-water.
Suitable solvents for this reaction are in particular organic aprotic solvents which dissolve the reactants but do not react with them. The condensation agents are inorganic bases, such as NaOH, KOH, NaOCH3 etc., but also organic bases, such as tertiary amines.
The following Examples illustrate methods of manufacturing a number of active compounds of the formula I. Further active compounds obtained in corresponding manner are listed in the following table.
These phenoxyphenoxyalkanecarboxylic acid derivatives of the formula I are stable compounds which are soluble in -conventional organic solvents, such as alcohols, ethers, ketones, dimethyl formamide, dimethyl sulphoxide etc.
10903~7 Example 1 34,1 g (0,1 mole) of 2-nitro-4-trifluoromethyl-3'-acetoxy-diphenyl ether are dissolved in 200 ml of acetic acid and equimolar amounts of chlorine are introduced into the solution at 40C with good stirring. The reaction course is followed by gas chromatography. When the reaction is complete, the resulting solution is poured into ice-water and extracted with toluene/ethyl acetate (1:1). The organic solvent is distilled off, giving an oil which is sapnnified with 30% methanolic sodium hydroxide solution to give the free phenol, The resulting oil has a boiling point of 159-165C at 0.03 mm Hg.
Yield: 23,5 g, 23.5 g of 2-nitro-4-trifluoromethyl-3'-hydroxy-4'-chloro-diphenyl ether are dissolved in 30 ml of ethyl methyl ketone, To this solution are added 18 ml of methyl 2-bromopropionate, 18 g of potassium carbonate and a trace of potassium bromide on the tip of a spatula, The reaction mixture is stirred overnight at a bath temperature of 80C, Insoluble constituents are removed by filtration and the solvent is distilled off, The residual oil is distilled in a high vacuum. Boiling point: 172C/
0,015 mm Hg, Yield: 20,8 g, CH
F3C ~ o _ ~ Cl ' : ' ~ ,-~' ' '; .... ':
-.
, . ': ', ' '' 1(1903~7 g Example 2 a) 68.2 g of 2-nitro-4-trimethyl-3'-acetoxy-diphenyl ether are dissolved in 80 ml of ethylene chloride and nitrating acid (1:1) is added dropwise at 0-5C. When the addition is complete, the reaction mixture is stirred for a further 1/2 hour and the reaction product is poured into water. The precipitated product is extracted with ethyl acetate/toluene (1:1). The solvent is distilled off, affording a solid product which is recrystallised from alcohol/water. Melting point: 129~-130C. Yield:
47 4 g (61.4% of theory).
b) 200 ml of methanol are added to 47.4 g of 2,4'-dinitro-4-trifluoromethyl-3'-acetoxy-diphenyl ether and, after addition of the equimolar amount of methanolic KOH, the reaction mixture is allowed to stand for half an hour.
The solvent is distilled off and the residue is dissolved in water. After acidification with 2N HCl, the precipitated phenol is extracted with ethyl acetate/
toluene (1:1). The solvent is dis~illed off, affording 44.5 g of an oil which crystallises on standing. Melting point: 78-79C.
c) 17.2 g of 2,4'-dinitro-4-trifluoromethyl-3'-hydroxy-diphenyl ether are dissolved in 50 ml of 2-butanone and, after addition of 13.4 g of methyl 2-bromopropionate, 13.8 g of potassium carbonate and a trace of potassium iodide on the tip of a spatula, the reaction mixture is stirred overnight at a bath temperature of 80C. The reaction mixture is subsequently filtered and the filtrate is concentrated. The residual oil is distilled in a high vacu~tm. Boiling point: 217C/0.05 torr. Yield:
6.2 g of the compound of the formula 1(J903t~7 F3C ~ ~ N02 R
R4 ~ o ~ R3 - . _ .. . _ _ _ _ Rl R2 R3 R4 A . Physical constant (~C) . .. _ _ .. . I
CH3 H Cl CF3 COOCH3 b.p.:~72/0.015 CH3 H Cl Cl COOCH3 oil CH3 H N02 CF3 COOCH3 b.p.:217/0.05 CH3 H Br CF3 COOCH3 CH3 H Br Cl COOCH3 CH3 H N02 Cl COOCH3 m.p. 87-88 CH3 H N02 CF3 Cooc~l2cH=cH2 CH3 H N02 Cl COSCH3 CH3 H Cl Cl COOC2H4N(C2H5 2 CH3 H Cl CF3 CN
CH3 H Cl CF3 Cooc2H4ocH3 b.p. 200/0~001 CH3 H N02 CF3 (C2H5)2 CH3 H Cl CF3 COOCH3 ~H3 H Cl CF3 COOH m;p. 168-170 CH3 H Cl Cl COOH m.p. 125 CH3 H N02 CF3 COOH r~
CH3 H Cl CF3 00~ Na ~b _ _ :. : .
. . . .
.: ', . .- ~ ' ~
. .
. . . . . . . .
. . . . . . .. .
90 3 ~ 7 . . .. . . .
Rl R2 R3 ~4 A Phys cal ._ . . __ _ . .
CH3 H Cl CN COOCH3 oil CH3 H N02 CN COOCH3 b.p. 188/0.35 CH3 H Cl CF3 CoocH2cH=cH2 b.p. 200-230/
CH3 H Cl CF3 COSCH2CH=CH2 0.001 CH3 H Cl Cl COOC2H5 nD5 1.5705 CH3 H Cl Cl . n25 1.5596 CH3 H Cl Cl COOiC4Hg nD5 1.5604 H H N02 CF3 COOCH3 m.p. 107-108 H H N02 CF3 COOH m,p, 98-104 C2H5 HCl CF3 COOCH3 CH3 H Br CF3 COOCH3 CH3 CH3 Cl CF3 COOC2H5 CH3 H Cl CF3 ; COSCH3 oil CH3 H Cl CF3 COOCH2 ~ .p,:235/O,OOl CH3 H Cl CF3 COOiC4Hg oil CH3 H Cl CF3 COOCH2CH2Cl oil CH3 H Cl CF3 COO-sec.C4Hg .p.:200/O,OOl CH3 H Cl CF3 COOn-C3H7 .p.:190/O,OOl CH3 H Cl CF3 COOCH2C_CH oil CH3 H Cl CF3 CoocH2cHc2H5 .p.:200/O,OOl CH3cH
CH3 H Cl CF3 COON=C ~ 3 oil . CH3 CH3 H Cl CF3 COO ~ oil CH3 H Cl CF3 CH3 oil ", ~ .
. . ~ .
.
Rl R2 R3 R4 A Physical , _ _ __ , , ,_, _ constant ( C) CH3 H Cl CF3 COOCH2CH2N~ .
CH3 H Cl CF3 2CH2cH3 CH3 H Cl CF3 CONH .
CH3 H Cl CF3 CO ~ . .
CH3 H Cl CF3 CO- ~ . .
CH3 H Cl CF3 CoocH2cH3 .
CH3 H Cl CF3 CONOCH~ oil CH3 H Cl CF3 COS ~ b.p.:230/O.OOl CH3 ~ Cl CF3 COO ~ il CH3 H Cl CF3 _ _ ~ .
.. . ...... .. ..
, ~ . - - -.. ~.. ... ~ . :
.' ' .
.. . ...
~ , . ' .
The invention also relates to herbicidal and plant growth-regulating compositions which contain a novel active compound of the formula I, as well as to methods of controlling weeds by pre- and post-emergent application and of inhibiting the growth of mono- and dicotyledonous plants, especially grasses, cereals, soya and tobacco shoots.
The compositions of the present invention can be in the conventional formulations.
The compositions of the present invention are ob-tained in known n~anner by homogeneously mixing and grinding active substances of the general formula I with suitable carriers, with or wi~hout the addition of dispersants or æolvents which are ine~-t to the active substances. The active substances can be processed to the following formulations:
solid formulations: -dusts, tracking powders, granules (coated granules, impregnated granules and homogeneous granules);
active subs~ance concentrates which are dispersible in water:
wettable powders, pastes, emulsions;
liquid formulations: solutions.
The concentration of active substance in the above described compositions is between 0.1 and 95%, preferably between 1 and 80%. Formulations can be diluted to c~ncentrations as low as 0.001%. The rates of application are ordinarily from 0.1 to 10 kg, preferably from 0.25 to 5 kg, of active substance per hectare. The active compounds of the formula I can be formulated for e~ample as follows (parts are by weight):
- 109(~ '7 Dusts: The following subs~ance are used to prepare a) 5% and b) 2% dust:
a) 5 parts of 2-chloro-5-~2'-nitro-4'-tri-fluoromethyl-phenoxy)--phenoxy-propionic acid methyl ester, parts of talci b) 2 parts of active substance ' 1 part of highly dispersed silicic acid 97 parts of talc.
The active substances are mixed with the carriers and ground.
Granulate: The following,su~stances are used to prepare a 5% granulate:
parts of the above active substance 0.25 part of epichlorohydrin -0.25 part of cetyl polyglycol ether 3.25 parts of polyethylene glycol ~ 1 parts of kaolin (particle size 0.3-0.8 mm).
,The active substance is mixed with epichlorohydrin and the mixture is dissolved in 6 parts of acetone. Then poly-ethylene glycol and cetyl polyglycol ether are added. The resulting solution is sprayed on kaolin and subsequently evaporated in vacuo.
Wettable Po~ders .
The following constituents are used for prepare a) a 50%, b) a 25% and c) a 10% wettable powder: -a) 50 parts of 2-chloro-5-(2'-nitro-4'-trifluoro-methyl-phenoxy)-a-phenoxy-propionic acid methyl ester, parts of sodium dibutylnaphthylsulphonate.
3 parts of naphthalenesulphonic acid/phenolsul-phonic acid/formaldehyde condensate (3:2:1), parts of kaolin, 22 parts of Champagne chalk;
.: ~ :, . . ......................... . -- - -.
1~90;~t~7 - b) 2~ parts of the above active substance, parts of sodium oleylmethyltauride, ; 2.5 parts of naphthalenesulphonic acid/formaldehyde condensate, 0.5 part of carboxymethyl cellulose, parts of neutral potassium aluminium silicate, 62 parts of kaolin;
c) 10 parts of the above active substance, 3 parts of a mix~ure of the sodium salts of saturated fatty alcohol sulphates, parts of naphthalenesulphonic acid/formaldehyde condensate.
82 parts of kaolin.
The indicated active substance is applied to the - corresponding carriers (kaolin and chalk) and then these are mixed and ground, to yield wettable powders of e~cellent wettability and suspension power. By diluting these we~table powders with water it is possible to obtain suspensions of the desired concentration of active substance. Such suspensions are used for controlling weeds and grass-like weeds in crops of cultivated plants by the preemergent method and for treating areas of grass.
~, ' 0 90 3 ~ 7 _ 16 -Paste . _ The following substances are used to manufacture a 45% paste: -parts of 2_chloro-5-(2'-nitro-4'-trifluoro-methyl phenox~)--phen~xy-propionic acid methyl ester, S parts of sodium aluminium silicate, 14 parts o cetyl polyglycol ether with 8 moles of the ethylene oxide, 1 part of oleyl polyglycol ether with 5 moles of the ethylene oxide,
2 parts of spindle oil, parts of polyethylene glycol, 23 parts of water.
- The active substance is homogeneously mixed with the adjuvants in appropriate devices and ground, yieldin~ a paste from which, by ~ilution with water, it is possible to obtain suspensions of the desired concentration o~
active substance. The suspensions are suitable for treating areas of grass.
Emulsifiable Concentrate The following ingredients are mixed to manufacture a 25% emulsifiable concentrate:
parts of 2_chloro-5-(2'-nitro-4'-trifluoro-methyl-phenoxy)-~-phenoxy-propionic acid methyl ester, - ~-.
parts of a mixture of nonylphenolpolyoxy- -ethoxy-ethylene and calcium dodecylenesul-phonate, 3S parts of 3,5,5-trimethyl-2-cyclohexan-1-one, parts of dimethyl formamide.
- . . ~ .. .. .
., - ~ , . -. : - - , , .
-' 10903G7 This concentrate can be diluted with water to give emulsions in the desired concentrations.
Instead of using the respective active substance indicated in the foregoing formulation examples, it is also possible to use another of the compounds comprised by the formula I.
The active substances contained in the compositions of the present invention influence the plant growth in different ways. Thus they inhibit, delay or prevent primarily the growth and germination. Their action is consequently both a pre- and post-emergent herbicidal and, growth-inhibiting action.
Compositions of the present invention, which contain as active component at least one compound of the formula I, are particularly suitable for inhibiting and controlling the growth of monocotyledonous and dicotyledonous plants,~-such as grasses, shrubs, trees, crops of cereals and legum-inous plants, sugar cane, tobacco plants, soya, onion and potato tubers, ornamentals, fruit trees and vines.
The primary effect attained by the compounds of the formula I consists in the desired reduction of the plant size, in particular of the growth in height. In general, a certain change in the form of the plant is allied to this reduction in size. As a direct consequence of the reduction of the growth in height the plant is strengthened: leaves and stems are better developed. By shortening the distances between internodes in monocotyledonous plants the breaking strength is increased. In this way it is possible to prevent to a great extent harvest losses caused by thunderstorms, prolonged rainfall etc., which usually result in a lodging of crops of cereals and leguminous plants, and thereby to facilitate harvesting. As side-effect, the reduced gro~th in height of useful plants results in a saving of fertilisers.
This also applied equally to ornamental plants and ornamental grass plots, turf for sporting activities, grass-covered " open spaces etc.
~.
.
, ~
One of the greatest problems posed by pure grass cultivations, however, is the actual cutting of the grass itself, whether in open spaces of urban areas, industrial sites, playing fields, along main roads, on airport runways, on railway embankments or the embankments of water bodies.
t In all these cases it is necessary to cut the turf or grass periodically. This operation is not only time-consuming, complicated and expensive in respect of labour and machinery, but involves the personnel concerned and traffic users in considerable hazard.
For this reason there is an urgent need in areas with extensive traffic networks to maintain and tend the grassy covering for strengthening road shoulders and embankments on traffic routes on the one hand, and on the other to keep it at a reasonable height by simple means during the entire vegetation period. This need is fulfilled in a very advantageous manner by applying the compounds of the formula I.
~n analogous fashion, the labour expended on cutting can be reduced by treating trees, shrubs and hedges, principally in urban and industrial areas, with the compounds of the present invention of the formula I.
The use of the active compounds of this invention of the formula I can also advantageously influence the growth of shoots and/or the fertility of fruit trees and vines.
Ornamental plants o pronounced growth in length can be reared as compact potted plants by treating them with the active compounds of this invention.
The active compounds of the formula I are also useful -' for inhibiting the growth of undesired suckers, for example in tobacco and ornamental plants, thereby avoiding the labour-consuming detaching of these suckers by hand. They are also useful for inhibiting the formation of shoots in stored tubers, for example those of ornamental plants, onions and -- ~9(~3~i7 - 19 _ potatoes, and inally for increasing the yield of cultivated plants with marked vegetative ~rowth, such as soya and sugar cane, by accelerating the transition from the vegetative to the generative growth phase by applying the active compounds of the invention.
Preferably the active compounds of the formula I are used to inhibit- the growth of grasses, cereal crops, tobacco plants, soya and ornamental plants.
The rates of application very and depend on the time of application. In general they are between 0.1 and 5 kg of active substance per hectare for. preemergence application and up to 4 kg per hectare for treating existing crops.
The facilitation of fruit abscission in the mechanical and manual harvesting of olives and citrus fruit has become of great ~conomic importance. Leaf abscission and defoliation is important in the harvesting of cotton.
The active substances of the present invention develop their action both via the parts of plants above the soil (contact action), especially the leaves, and via the soil, as preemergent herbicide (inhibition of germination).
The action of the compounds of the formula I as strong growth inhibitors is evident from the fact that most of the species of plants treated in the post-emergent state exhibit stationary growth after a test period of three weeks, whilst the treated parts of the plants assume a dark green colouration. The leaves, however, do not drop.
In some plant species this growth inhibition occurs even at a rate of application of 0.5 kg/ha and below. As not all plant species are equally strongly inhibited in their growth, a selective use is possible by choosing a specific low rate of application.
The active substances of the invention are also of interest for combination with a number of herbicides of the phenylurea and triazine series for use in cereal crops, maize, sugar cane, and in fruit culture and viticulture.
~ ' .: -. .
:
In areas where there is a high risk of erosion, the active substances of the invention can be used as growth inhibitors in a very wide variety of crops. The weed cover is not eliminated, but only so strongly inhibited that it no longer competes with the cultivated plants.
In addition, the active substances of the formula I
are distinguished by a very pronounced preemergent herbicidal action and are thus also strong germination inhibitors.
The- following test methods were employed to establish the usefulness of the compounds of the formula I as herbicides (pre- and postemergen~).
Preemer~,ent herb idal action_~ermination inhibition) In a greenhouse, imrnediately after sowing the test plants in seed dishes the surface of the soil is treated with an aqueous suspension of the active substances obtained from a 25% wettable powder. Four different concentration series were used, corresponding to 4, 2, 1 and 0.5 kg of active substance per hectare respectively. The seed dishes are kept in the greenhouse at 22-25C and 50 to 70% relative humidity. The test is evaluated 3 weeks later according to the following rating:
1 ~ plants have not germinated or are totally w~thered 2-8 = intermediate stages of damage 9 = plants undamaged (as untreated control).
Post-emer~ent herbicidal action (Contact herbicide) A large number (at least 7) of weeds and cultivated plants, both mono- and dicotyledonous, were sprayed after emergence in the 4- to 6-leaf stage with an aqueous active substance emulsion in rates to 0.5, 1, 2 and 4 kg of active substance per hectare and kept at 24-26C and 45-60% rela~ive humidity.
The test was evaluated, as in the preemergent test, 5 and 15 days after treatment in accordance with the same rating.
The tested compounds of the present invention had a strong .. . . . -.
.. ~ . ...
. .
- . : .
..
' 109 ~ 3 ~7 _ 21 -contact herbicidal action on some plants and in many others effected stationary growth as a symptom of the growth-inhibiting properties.
Growth inhibition in ~rasses Seeds of the grasses Lolium perenne, Poa pratensis, Festuca ovina, and Dactylis glomerata were so~.~n in plastic dishes filled with an earth/turf/sand mixture (6:3:1). The emergent grasses were cut back weekly to a height of 4 cln above the soil and 1 day after the last cut were sprayed with aqueous spray mixtures of an active substance of the formula I. The amount of active substance corresponded to a rate of appli-cation o~ 5 kg of active substance per hectare. The growth of the grasses was evaluated 10 and 21 days after appli-cation.
Growth _nhibition in cereals Spring wheat (Triticum aestivum), summer barley (Hordeum vul-gare) and rye (Secale) was sown in sterilised soil in plastic beakers and reared in a greenhouse. The cereal shoots were treated 5 days after sowing with a spray broth of the active substance. The leaf application corresponded to 6 kg of active substance per hectare. Evaluation is made 21 days later.
- The active substance is homogeneously mixed with the adjuvants in appropriate devices and ground, yieldin~ a paste from which, by ~ilution with water, it is possible to obtain suspensions of the desired concentration o~
active substance. The suspensions are suitable for treating areas of grass.
Emulsifiable Concentrate The following ingredients are mixed to manufacture a 25% emulsifiable concentrate:
parts of 2_chloro-5-(2'-nitro-4'-trifluoro-methyl-phenoxy)-~-phenoxy-propionic acid methyl ester, - ~-.
parts of a mixture of nonylphenolpolyoxy- -ethoxy-ethylene and calcium dodecylenesul-phonate, 3S parts of 3,5,5-trimethyl-2-cyclohexan-1-one, parts of dimethyl formamide.
- . . ~ .. .. .
., - ~ , . -. : - - , , .
-' 10903G7 This concentrate can be diluted with water to give emulsions in the desired concentrations.
Instead of using the respective active substance indicated in the foregoing formulation examples, it is also possible to use another of the compounds comprised by the formula I.
The active substances contained in the compositions of the present invention influence the plant growth in different ways. Thus they inhibit, delay or prevent primarily the growth and germination. Their action is consequently both a pre- and post-emergent herbicidal and, growth-inhibiting action.
Compositions of the present invention, which contain as active component at least one compound of the formula I, are particularly suitable for inhibiting and controlling the growth of monocotyledonous and dicotyledonous plants,~-such as grasses, shrubs, trees, crops of cereals and legum-inous plants, sugar cane, tobacco plants, soya, onion and potato tubers, ornamentals, fruit trees and vines.
The primary effect attained by the compounds of the formula I consists in the desired reduction of the plant size, in particular of the growth in height. In general, a certain change in the form of the plant is allied to this reduction in size. As a direct consequence of the reduction of the growth in height the plant is strengthened: leaves and stems are better developed. By shortening the distances between internodes in monocotyledonous plants the breaking strength is increased. In this way it is possible to prevent to a great extent harvest losses caused by thunderstorms, prolonged rainfall etc., which usually result in a lodging of crops of cereals and leguminous plants, and thereby to facilitate harvesting. As side-effect, the reduced gro~th in height of useful plants results in a saving of fertilisers.
This also applied equally to ornamental plants and ornamental grass plots, turf for sporting activities, grass-covered " open spaces etc.
~.
.
, ~
One of the greatest problems posed by pure grass cultivations, however, is the actual cutting of the grass itself, whether in open spaces of urban areas, industrial sites, playing fields, along main roads, on airport runways, on railway embankments or the embankments of water bodies.
t In all these cases it is necessary to cut the turf or grass periodically. This operation is not only time-consuming, complicated and expensive in respect of labour and machinery, but involves the personnel concerned and traffic users in considerable hazard.
For this reason there is an urgent need in areas with extensive traffic networks to maintain and tend the grassy covering for strengthening road shoulders and embankments on traffic routes on the one hand, and on the other to keep it at a reasonable height by simple means during the entire vegetation period. This need is fulfilled in a very advantageous manner by applying the compounds of the formula I.
~n analogous fashion, the labour expended on cutting can be reduced by treating trees, shrubs and hedges, principally in urban and industrial areas, with the compounds of the present invention of the formula I.
The use of the active compounds of this invention of the formula I can also advantageously influence the growth of shoots and/or the fertility of fruit trees and vines.
Ornamental plants o pronounced growth in length can be reared as compact potted plants by treating them with the active compounds of this invention.
The active compounds of the formula I are also useful -' for inhibiting the growth of undesired suckers, for example in tobacco and ornamental plants, thereby avoiding the labour-consuming detaching of these suckers by hand. They are also useful for inhibiting the formation of shoots in stored tubers, for example those of ornamental plants, onions and -- ~9(~3~i7 - 19 _ potatoes, and inally for increasing the yield of cultivated plants with marked vegetative ~rowth, such as soya and sugar cane, by accelerating the transition from the vegetative to the generative growth phase by applying the active compounds of the invention.
Preferably the active compounds of the formula I are used to inhibit- the growth of grasses, cereal crops, tobacco plants, soya and ornamental plants.
The rates of application very and depend on the time of application. In general they are between 0.1 and 5 kg of active substance per hectare for. preemergence application and up to 4 kg per hectare for treating existing crops.
The facilitation of fruit abscission in the mechanical and manual harvesting of olives and citrus fruit has become of great ~conomic importance. Leaf abscission and defoliation is important in the harvesting of cotton.
The active substances of the present invention develop their action both via the parts of plants above the soil (contact action), especially the leaves, and via the soil, as preemergent herbicide (inhibition of germination).
The action of the compounds of the formula I as strong growth inhibitors is evident from the fact that most of the species of plants treated in the post-emergent state exhibit stationary growth after a test period of three weeks, whilst the treated parts of the plants assume a dark green colouration. The leaves, however, do not drop.
In some plant species this growth inhibition occurs even at a rate of application of 0.5 kg/ha and below. As not all plant species are equally strongly inhibited in their growth, a selective use is possible by choosing a specific low rate of application.
The active substances of the invention are also of interest for combination with a number of herbicides of the phenylurea and triazine series for use in cereal crops, maize, sugar cane, and in fruit culture and viticulture.
~ ' .: -. .
:
In areas where there is a high risk of erosion, the active substances of the invention can be used as growth inhibitors in a very wide variety of crops. The weed cover is not eliminated, but only so strongly inhibited that it no longer competes with the cultivated plants.
In addition, the active substances of the formula I
are distinguished by a very pronounced preemergent herbicidal action and are thus also strong germination inhibitors.
The- following test methods were employed to establish the usefulness of the compounds of the formula I as herbicides (pre- and postemergen~).
Preemer~,ent herb idal action_~ermination inhibition) In a greenhouse, imrnediately after sowing the test plants in seed dishes the surface of the soil is treated with an aqueous suspension of the active substances obtained from a 25% wettable powder. Four different concentration series were used, corresponding to 4, 2, 1 and 0.5 kg of active substance per hectare respectively. The seed dishes are kept in the greenhouse at 22-25C and 50 to 70% relative humidity. The test is evaluated 3 weeks later according to the following rating:
1 ~ plants have not germinated or are totally w~thered 2-8 = intermediate stages of damage 9 = plants undamaged (as untreated control).
Post-emer~ent herbicidal action (Contact herbicide) A large number (at least 7) of weeds and cultivated plants, both mono- and dicotyledonous, were sprayed after emergence in the 4- to 6-leaf stage with an aqueous active substance emulsion in rates to 0.5, 1, 2 and 4 kg of active substance per hectare and kept at 24-26C and 45-60% rela~ive humidity.
The test was evaluated, as in the preemergent test, 5 and 15 days after treatment in accordance with the same rating.
The tested compounds of the present invention had a strong .. . . . -.
.. ~ . ...
. .
- . : .
..
' 109 ~ 3 ~7 _ 21 -contact herbicidal action on some plants and in many others effected stationary growth as a symptom of the growth-inhibiting properties.
Growth inhibition in ~rasses Seeds of the grasses Lolium perenne, Poa pratensis, Festuca ovina, and Dactylis glomerata were so~.~n in plastic dishes filled with an earth/turf/sand mixture (6:3:1). The emergent grasses were cut back weekly to a height of 4 cln above the soil and 1 day after the last cut were sprayed with aqueous spray mixtures of an active substance of the formula I. The amount of active substance corresponded to a rate of appli-cation o~ 5 kg of active substance per hectare. The growth of the grasses was evaluated 10 and 21 days after appli-cation.
Growth _nhibition in cereals Spring wheat (Triticum aestivum), summer barley (Hordeum vul-gare) and rye (Secale) was sown in sterilised soil in plastic beakers and reared in a greenhouse. The cereal shoots were treated 5 days after sowing with a spray broth of the active substance. The leaf application corresponded to 6 kg of active substance per hectare. Evaluation is made 21 days later.
Claims (7)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. Phenoxyphenoxyalkanecarboxylic acid derivatives of the formula I
(I) wherein R1 represents hydrogen or C1-C4 alkyl, R2 represents hydrogen or C1-C4 alkyl, R3 represents halogen, or nitro, R4 represents halogen, cyano or trifluoromethyl, A represents cyano or the group -COB, B represents a radical OR5 or SR6, R5 represents hydrogen or the cation of a base ? M n?, wherein M represents an alkali metal or alkaline earth metal cation or an ammonio radical n as integer 1, 2 or 3 corresponds to the valency of the cation, whilst Ra, Rb, Rc and Rd, each independently of the other, represent hydrogen, benzyl or an alkyl radical which is unsubstituted or substituted by -CH, -NH2 or C1-C4 alkoxy; and R5 further represents, -a C1 - C8 alkyl radical which is unsubstituted or substituted by halogen, cyano, nitro, hydroxyl or a C2-C8 alkyl radical which can be interrupted by oxygen, sulphur, nitrogen, carbonyl or carbonyloxy, -a C3-C6 cycloalkyl radical, -a C3-C6 alkenyl or alkynyl radical which can be substituted by halogen, -a phenyl or benzyl radical which can be substituted by halogen, cyano, nitro, C1-C4 alkyl, C1-C4 alkoxy or trifluoromethyl, and R6 represents a C1-C8 alkyl radical which can be substituted by halogen, cyano, nitro or hydroxyl or interrupted by oxygen, sulphur, nitrogen, carbonyl or carbonyloxy, -a C3-C6 cycloalkyl radical, -a C3-C6 alkenyl or alkynyl radical which can be substituted by halogen, -a phenyl or benzyl radical which can be substituted by halogen, cyano, nitro, C1-C4 alkyl, C1-C4 alkoxy or trifluoromethyl.
(I) wherein R1 represents hydrogen or C1-C4 alkyl, R2 represents hydrogen or C1-C4 alkyl, R3 represents halogen, or nitro, R4 represents halogen, cyano or trifluoromethyl, A represents cyano or the group -COB, B represents a radical OR5 or SR6, R5 represents hydrogen or the cation of a base ? M n?, wherein M represents an alkali metal or alkaline earth metal cation or an ammonio radical n as integer 1, 2 or 3 corresponds to the valency of the cation, whilst Ra, Rb, Rc and Rd, each independently of the other, represent hydrogen, benzyl or an alkyl radical which is unsubstituted or substituted by -CH, -NH2 or C1-C4 alkoxy; and R5 further represents, -a C1 - C8 alkyl radical which is unsubstituted or substituted by halogen, cyano, nitro, hydroxyl or a C2-C8 alkyl radical which can be interrupted by oxygen, sulphur, nitrogen, carbonyl or carbonyloxy, -a C3-C6 cycloalkyl radical, -a C3-C6 alkenyl or alkynyl radical which can be substituted by halogen, -a phenyl or benzyl radical which can be substituted by halogen, cyano, nitro, C1-C4 alkyl, C1-C4 alkoxy or trifluoromethyl, and R6 represents a C1-C8 alkyl radical which can be substituted by halogen, cyano, nitro or hydroxyl or interrupted by oxygen, sulphur, nitrogen, carbonyl or carbonyloxy, -a C3-C6 cycloalkyl radical, -a C3-C6 alkenyl or alkynyl radical which can be substituted by halogen, -a phenyl or benzyl radical which can be substituted by halogen, cyano, nitro, C1-C4 alkyl, C1-C4 alkoxy or trifluoromethyl.
2. The compounds of the formula I according to claim 1, wherein R1 represents hydrogen and A, R2, R3 and R4 are as defined in formula I.
3. The compounds of the formula I according to claim 1, wherein A
represents -COB, B represents -OR5 and R1 represents hydrogen, and R2, R3, R4 and R5 are as defined in formula I.
represents -COB, B represents -OR5 and R1 represents hydrogen, and R2, R3, R4 and R5 are as defined in formula I.
4. The compounds of the formula I according to claim 1, wherein A
represents -COB, B represents -SR6 and R1 represents hydrogen, and R2, R3, R4 and R6 are as defined in formula I.
represents -COB, B represents -SR6 and R1 represents hydrogen, and R2, R3, R4 and R6 are as defined in formula I.
5. .alpha.-[2-Chloro-5-(2'-nitro-4'-trifluoromethyl(phenoxy)-phenoxy]
propionic acid methyl ester.
propionic acid methyl ester.
6. A method of controlling weeds at a locus, which comprises applying to said locus an effective amount of a compound of the formula I according to claim 1 or of a composition containing such a compound.
7. A method of regulating the growth of plants which comprises applying to the plants an effective amount of a compound of the formula I
according to claim 1 or of a composition containing such a compound.
according to claim 1 or of a composition containing such a compound.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH8068/77 | 1977-06-30 | ||
| CH806877 | 1977-06-30 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1090367A true CA1090367A (en) | 1980-11-25 |
Family
ID=4334639
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA306,425A Expired CA1090367A (en) | 1977-06-30 | 1978-06-28 | Phenoxyphenoxyalkanecarboxylic acid derivatives having a herbicidal and plant growth regulating action |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0000474B1 (en) |
| JP (1) | JPS5416436A (en) |
| CA (1) | CA1090367A (en) |
| DE (1) | DE2860339D1 (en) |
| ES (1) | ES471398A1 (en) |
| IL (1) | IL55029A (en) |
| IT (1) | IT7825138A0 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2850902A1 (en) * | 1978-11-24 | 1980-06-12 | Hoechst Ag | NEW PHENOXY-PHENOXI-PROPIONIC ACID AMIDES AND THEIR USE AS HERBICIDES |
| US4309210A (en) * | 1978-12-01 | 1982-01-05 | Ciba-Geigy Corporation | Preemergence method of selectively controlling weeds in crops of cereals and composition therefor |
| EP0078536A3 (en) * | 1981-11-02 | 1983-07-27 | Sandoz Ag | Phosphinates and phosphonates and their use in the control of weeds |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1560416A (en) * | 1975-09-03 | 1980-02-06 | Rohm & Haas | Trifluoromethylphenyl derivatives |
| NZ181994A (en) * | 1975-09-27 | 1978-09-20 | Ishihara Sangyo Kaisha | (2-chloro-4-trifluorom-ethylphenoxy)-phenoxy acids,esters,ethers,amides and nitriles and herbicidal compositions |
| GB1565972A (en) * | 1976-04-15 | 1980-04-23 | Sori Soc Rech Ind | M-substituted phenoxypropionic acid dervatives |
| DE2632581C2 (en) * | 1976-07-20 | 1982-07-15 | Hoechst Ag, 6000 Frankfurt | Substituted nitrodiphenyl ethers, processes for their preparation and herbicidal compositions containing them |
| AU2716177A (en) * | 1976-07-21 | 1979-01-25 | Ciba Geigy Ag | Herbicides |
-
1978
- 1978-06-22 DE DE7878100218T patent/DE2860339D1/en not_active Expired
- 1978-06-22 EP EP78100218A patent/EP0000474B1/en not_active Expired
- 1978-06-28 IL IL55029A patent/IL55029A/en unknown
- 1978-06-28 CA CA306,425A patent/CA1090367A/en not_active Expired
- 1978-06-29 IT IT7825138A patent/IT7825138A0/en unknown
- 1978-06-29 ES ES471398A patent/ES471398A1/en not_active Expired
- 1978-06-30 JP JP8044678A patent/JPS5416436A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| EP0000474A1 (en) | 1979-02-07 |
| IT7825138A0 (en) | 1978-06-29 |
| EP0000474B1 (en) | 1980-11-26 |
| IL55029A (en) | 1982-09-30 |
| IL55029A0 (en) | 1978-08-31 |
| DE2860339D1 (en) | 1981-02-12 |
| ES471398A1 (en) | 1979-02-01 |
| JPS5416436A (en) | 1979-02-07 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |