CA1114382A - Esters of 0-(pyridyloxy-phenyl)-lactic acids - Google Patents
Esters of 0-(pyridyloxy-phenyl)-lactic acidsInfo
- Publication number
- CA1114382A CA1114382A CA330,939A CA330939A CA1114382A CA 1114382 A CA1114382 A CA 1114382A CA 330939 A CA330939 A CA 330939A CA 1114382 A CA1114382 A CA 1114382A
- Authority
- CA
- Canada
- Prior art keywords
- formula
- phenyl
- acid
- ester
- oxy
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/62—Oxygen or sulfur atoms
- C07D213/63—One oxygen atom
- C07D213/64—One oxygen atom attached in position 2 or 6
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/62—Oxygen or sulfur atoms
- C07D213/63—One oxygen atom
- C07D213/64—One oxygen atom attached in position 2 or 6
- C07D213/643—2-Phenoxypyridines; Derivatives thereof
-
- 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
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
Abstract
Abstract of the Disclosure The present invention relates to novel esters of O-(pyridyloxy-phenyl)-lactic acids which have a herbicidal action and a plant-growth-regulating action, which esters correspond to the formula I
in whlch "Hal" is a halogen atom, X is hydrogen or a halogen atom, Y is an oxygen or sulfur atom, Z is a C1-C4-alkyl group which is unsubstituted or is substituted by methyl, ethyl, cyano, methylcarbonyl, or by the group -COQ, and Q is an -OH or SH group, the salt of a carbonyl or thiocarbonyl acid, or an ester function, thioester function or amide function.
in whlch "Hal" is a halogen atom, X is hydrogen or a halogen atom, Y is an oxygen or sulfur atom, Z is a C1-C4-alkyl group which is unsubstituted or is substituted by methyl, ethyl, cyano, methylcarbonyl, or by the group -COQ, and Q is an -OH or SH group, the salt of a carbonyl or thiocarbonyl acid, or an ester function, thioester function or amide function.
Description
Case 5-11795/~
~ .
It is known rom the prior art that substituted phenoxy-propionic acid derivatives can be used as :
herbicides (see R. Wegler, Chemie der Pflanzenschutz-und Sch~dlingsbek~mpfungsmittel [Chemistry of plant protective agents and pesticidal compositionsl, Springer-Verlag, Heidelberg, New York, 1970, Volume 2, pp. 278 ff, and more recent patent applications, such as German Offenlegungsschriften Nos. ~,223,894 an~ 2,613,697, and B~lgian Patent Application No. 855,~94.
The herbicidal effectiveness of the known compounds does not however always satisfy requirements, particularly when these compounds are applied in small amounts.
Furthermore, such compounds are frequently not suf~iently selective with regard to the cultivated plants to be protected. Attempts have already been made to overcome the stated shortcomings of the known propionic acid derivatives by incorporation of suitable functional groups in the ester part o~ the molecule. In conn ction with this work, there have also become known substitut~d phenoxy-propionic acid derivatives which carry in the ester part of the molPcule a~ additional alkoxycarbonyl (COOalkyl) or a carboxyl group (COOH) (see German O~fen-~, ..~
.
.; . , . , - .
.
~ 3~ ~ .
~ .
It is known rom the prior art that substituted phenoxy-propionic acid derivatives can be used as :
herbicides (see R. Wegler, Chemie der Pflanzenschutz-und Sch~dlingsbek~mpfungsmittel [Chemistry of plant protective agents and pesticidal compositionsl, Springer-Verlag, Heidelberg, New York, 1970, Volume 2, pp. 278 ff, and more recent patent applications, such as German Offenlegungsschriften Nos. ~,223,894 an~ 2,613,697, and B~lgian Patent Application No. 855,~94.
The herbicidal effectiveness of the known compounds does not however always satisfy requirements, particularly when these compounds are applied in small amounts.
Furthermore, such compounds are frequently not suf~iently selective with regard to the cultivated plants to be protected. Attempts have already been made to overcome the stated shortcomings of the known propionic acid derivatives by incorporation of suitable functional groups in the ester part o~ the molecule. In conn ction with this work, there have also become known substitut~d phenoxy-propionic acid derivatives which carry in the ester part of the molPcule a~ additional alkoxycarbonyl (COOalkyl) or a carboxyl group (COOH) (see German O~fen-~, ..~
.
.; . , . , - .
.
~ 3~ ~ .
- 2 -legungsschift No. 2,628,384.
The present invention relates to novel esters of O~(pyridyloxy~phenyl)-lactic acids having a herbicidal and plant-growth regula~ing action, to F)rocesses for producing these esters, to compositions containing them as active substances, and to the use of these esters, or of composition~ containing them, for combating weeds and for regulating plant growth.
Surprisingly, the active substances of the formula I
according to the invention are superior to the hitherto known compounds of the prior art which have a similar structure and which are substituted in the ester part by an additional ester functionn The novel active sub-stances are distinguished by a high activity against numerous weeds. Furthermore, they are selective with respect to important cultivated plants, for example wheat, soya bean, cotton and sugar beet.
The novel active substaQces of the present invention are 0-[4-(5'-halogenopyridyl-2'-oxy)-phenyl)-lactic acid esters and correspond to the formula I
~al_~-O~ O-C~-CU-Y-Z-CO-Q (I) in which "Hal" is a halogen atom, X is hydrogen or a halogen atom, Y is an oxygen or sulfur atom, Z is a Cl-C4 alkylene group which is unsubstitutPd or substituted by methyl, ethyl, cyano, methyLcarbonyl or by a group -COQ, :
P 1~ SR2 or -NR3R4, wherein .
~; ' ' ~ ' '. ' !
~L43~
Rl, R2, R3 and R4 independently of one another are each hydrogen or C1 to C~-alkyl.
The novel compounds of the formula I are produced by known reactions of chemical synthesis, for example according to one of the following reaction patterns:
(a) X CH3 Hal ~ ~ O OH ~ Hal-CH-CO-Y-Z~CO-Q~
N
A correspondingly substituted 4_(s t -halogenopyridyl-2'-oxy)-phenol is reacted, in the presence of a base as an acid-binding agent, advantageously in an i~nert sol~ent, w~th an appropriate lQ derivative of 2-halogenopropionic acid, where "Hal" is a halogen atom, preferably chlori~ne or bromi`ne, and X, Y and Z have the meanings defined under the formula r.
4-(5'-Halogenopyridyl-2'-oxyl-p~lenol is o~tained by reaction of appropriately substituted 2,5-dihalogenopyridines with hydroquinone in a manner known per se, ~' .
," ~1 .
,, :
' k: ~
The derivatives of ~-halogenopropionic acid are obtained in a manner known per se by reaction of hydroxycarboxylic acid, or mercaptocarboxylic acid derivatives, with 2-halogenopropionic acid halides.
b) X
Hal ~ ~ OC3-COOYH ~ Hal-Z-C0-Q~
The 0-[4-(5'-halogenopyridyl-2' oxy)-phenyll-lactic acids or -thiolic acids known from the prior art (see for example German 0ffenlegungsschrift No. 2,546,251 or No. 2,732 9 846) are reacted in a known manner, in the presence of a base as acid-binding agent, with esters of halogenocarboxylic aci.ds. These esters correspond to the formula Hal - Z - C0 - Q
wherein "Hal?' is a halogen atom, preferably chlorine or bromine, and Q and Z have the meanings defined under the formula I, and are, for example, esters, thioesters or amides of chloroacetic acid, bromoacetic acid, a-bromo-propionic acid, ~-bromobutyxic acid, ~-chloro- or -bromo-propionic acid, ~-bromobutyric acid, ~-bromobutyric acid, and so forth.
c), X
~81 ~ ~ 3 base ~ ~ 0 ~ 0CH-C0Hal + HY-Z~C0-Q ~
In this modification of the above process, acid halides of 0-[4-(5' halogenopyridyl-2' oxy)-phenyl]-lactic acids are reac~ed, in a manner known per se, with esters of hydroxy- or mercaptocarboxylic acids. Examples ;: ~
... . . . . .
.. ~ , . . .
?
` ~
of acids of this type are lactic acid, glycolic acid, ~-hydroxypropionic acid, ~- or ~-hydroxybutyric acids, and also the corresponding thiolic acids, thioglycolic acid, thiolactic acid, and so forth.
The reactions are preferably performed in a solvent which is inert to the reactants. Suitable solvents are solvents belonging to the widest variety of classes of substances, such as aliphatic and aromat:ic, optionally chlorinated hydrocarbons, for example ethylene chloride, and the like, as well as polar organic solvents, such as ethers, ketones, amides, stable esters, for example methyl ethyl ketone, dimethoxyethane, dimethylformamide, dimethyl sulfoxide, tetrahydrofuran, and so forth.
As basic acid acceptors for the reaction with halogen compounds, it is possible to use aqueous alkali metal hydroxides, such as KOH and NaOH, and also further customary basic substances, such as carbonates (K2CO3, NaHCO3), alcoholates (NaOCH3 and potassium tert-butylate), but also organic bases, such as triethylamine, and so on.
The free propionthiolic acid (Y - S) to be used for example as starting material in reaction pa~tern b), and also the production ~hereof from the correspon~ing propionic acid halide with hydrogen sulfide, Na2S or NaHS, in the pre~ence of a basic acid acceptor, is the subject matter o a pending patent application. The a-~4-(3',5'-dichloropyridyl-(2')-oxy)-phenoxy]-propion-thiolic acid produced by this method ls an oil having a refractive index n21 = 1.5787, which melts at 85-87C
after crystallisa~ion.
The Examples which follow illustrate the production of some active substances of the formula I according to the invention. Further final substances o~ the formula I
~ 4L3~ :
~,~
which are produced in a corresponding manner or by another of the methods mentioned in the text are subsequently listed in tabular form.
Example 1 0-[4-(3',5'-Dichloropyridyl-2'-oxy)-phenyl]-thiollactic acid methoxycarbonylmethyl)-ester Cl Cl ~ 0 ~ OCH-C=0 SC~2C~OcH3 5.8 g (0.055 mol) of thioglycolic acid methyl ester and 5.5 g (0.055 mol) of triethylamine are added to 17.3 g (0.05 mol) of 0-[4-(3',5'-dichloropyridyl-2'-oxy)-phenyll-lactlc acid chloride in 130 ml of toluene. A~ter the exothermic reaction has subsided, the mixture is heated for 2 hours at 40C. The reaction is then cooled, the salt is filtered off, and the filtrate is concen-trated by evaporation and filtered in chloroform through a short silica gel column. Concentration by evaporation leaves 13.5 g (64.8 % of theory) of the title product in the form of oil having a refractive index n25 = 1.5580, and this product melts at 65C after recrystallisation form ether/petroleum ether.
The acid chloride required as starting material is obtained as follows: , 30 ml of thionyl chloride is added to 26.8 g (0.082 mol) of 0-[4-(3',5'-dichloropyridyl-2'-oxy)-phenyl]-lactic acid and, after the evolution of gas has subsi~ed, the mixture is heated to 50C. After two hours, the reaction mixture is concentrated in vacuo; 100 ml of toluene .
: . . .: ' . ' . . .
. : .
. .
~ ` 1 f~ 3~ 2 is added and the mixture is again concentrated by evapor-ation. There is obtained as product a dark-brown oil, which slowly commences to crystallise. The yield is 25.9 g (86.7% of theory) o 0-[4-(3',5'-dichloropyridyl-2'-oxy)-phenyl~-lactic acid chloride having a melting point of 45C.
0-[4-(3',5' Dichloropyridyl-2'-oxy)-pherlyl]-thioLartic acid-(l"-methoxycarbonyl-ethyl)-ester , .. . ,. .. _ _ _ . ____ . ~
~1 Cl ~ 0 ~ -CH-C0-SCH-COOCH
The present invention relates to novel esters of O~(pyridyloxy~phenyl)-lactic acids having a herbicidal and plant-growth regula~ing action, to F)rocesses for producing these esters, to compositions containing them as active substances, and to the use of these esters, or of composition~ containing them, for combating weeds and for regulating plant growth.
Surprisingly, the active substances of the formula I
according to the invention are superior to the hitherto known compounds of the prior art which have a similar structure and which are substituted in the ester part by an additional ester functionn The novel active sub-stances are distinguished by a high activity against numerous weeds. Furthermore, they are selective with respect to important cultivated plants, for example wheat, soya bean, cotton and sugar beet.
The novel active substaQces of the present invention are 0-[4-(5'-halogenopyridyl-2'-oxy)-phenyl)-lactic acid esters and correspond to the formula I
~al_~-O~ O-C~-CU-Y-Z-CO-Q (I) in which "Hal" is a halogen atom, X is hydrogen or a halogen atom, Y is an oxygen or sulfur atom, Z is a Cl-C4 alkylene group which is unsubstitutPd or substituted by methyl, ethyl, cyano, methyLcarbonyl or by a group -COQ, :
P 1~ SR2 or -NR3R4, wherein .
~; ' ' ~ ' '. ' !
~L43~
Rl, R2, R3 and R4 independently of one another are each hydrogen or C1 to C~-alkyl.
The novel compounds of the formula I are produced by known reactions of chemical synthesis, for example according to one of the following reaction patterns:
(a) X CH3 Hal ~ ~ O OH ~ Hal-CH-CO-Y-Z~CO-Q~
N
A correspondingly substituted 4_(s t -halogenopyridyl-2'-oxy)-phenol is reacted, in the presence of a base as an acid-binding agent, advantageously in an i~nert sol~ent, w~th an appropriate lQ derivative of 2-halogenopropionic acid, where "Hal" is a halogen atom, preferably chlori~ne or bromi`ne, and X, Y and Z have the meanings defined under the formula r.
4-(5'-Halogenopyridyl-2'-oxyl-p~lenol is o~tained by reaction of appropriately substituted 2,5-dihalogenopyridines with hydroquinone in a manner known per se, ~' .
," ~1 .
,, :
' k: ~
The derivatives of ~-halogenopropionic acid are obtained in a manner known per se by reaction of hydroxycarboxylic acid, or mercaptocarboxylic acid derivatives, with 2-halogenopropionic acid halides.
b) X
Hal ~ ~ OC3-COOYH ~ Hal-Z-C0-Q~
The 0-[4-(5'-halogenopyridyl-2' oxy)-phenyll-lactic acids or -thiolic acids known from the prior art (see for example German 0ffenlegungsschrift No. 2,546,251 or No. 2,732 9 846) are reacted in a known manner, in the presence of a base as acid-binding agent, with esters of halogenocarboxylic aci.ds. These esters correspond to the formula Hal - Z - C0 - Q
wherein "Hal?' is a halogen atom, preferably chlorine or bromine, and Q and Z have the meanings defined under the formula I, and are, for example, esters, thioesters or amides of chloroacetic acid, bromoacetic acid, a-bromo-propionic acid, ~-bromobutyxic acid, ~-chloro- or -bromo-propionic acid, ~-bromobutyric acid, ~-bromobutyric acid, and so forth.
c), X
~81 ~ ~ 3 base ~ ~ 0 ~ 0CH-C0Hal + HY-Z~C0-Q ~
In this modification of the above process, acid halides of 0-[4-(5' halogenopyridyl-2' oxy)-phenyl]-lactic acids are reac~ed, in a manner known per se, with esters of hydroxy- or mercaptocarboxylic acids. Examples ;: ~
... . . . . .
.. ~ , . . .
?
` ~
of acids of this type are lactic acid, glycolic acid, ~-hydroxypropionic acid, ~- or ~-hydroxybutyric acids, and also the corresponding thiolic acids, thioglycolic acid, thiolactic acid, and so forth.
The reactions are preferably performed in a solvent which is inert to the reactants. Suitable solvents are solvents belonging to the widest variety of classes of substances, such as aliphatic and aromat:ic, optionally chlorinated hydrocarbons, for example ethylene chloride, and the like, as well as polar organic solvents, such as ethers, ketones, amides, stable esters, for example methyl ethyl ketone, dimethoxyethane, dimethylformamide, dimethyl sulfoxide, tetrahydrofuran, and so forth.
As basic acid acceptors for the reaction with halogen compounds, it is possible to use aqueous alkali metal hydroxides, such as KOH and NaOH, and also further customary basic substances, such as carbonates (K2CO3, NaHCO3), alcoholates (NaOCH3 and potassium tert-butylate), but also organic bases, such as triethylamine, and so on.
The free propionthiolic acid (Y - S) to be used for example as starting material in reaction pa~tern b), and also the production ~hereof from the correspon~ing propionic acid halide with hydrogen sulfide, Na2S or NaHS, in the pre~ence of a basic acid acceptor, is the subject matter o a pending patent application. The a-~4-(3',5'-dichloropyridyl-(2')-oxy)-phenoxy]-propion-thiolic acid produced by this method ls an oil having a refractive index n21 = 1.5787, which melts at 85-87C
after crystallisa~ion.
The Examples which follow illustrate the production of some active substances of the formula I according to the invention. Further final substances o~ the formula I
~ 4L3~ :
~,~
which are produced in a corresponding manner or by another of the methods mentioned in the text are subsequently listed in tabular form.
Example 1 0-[4-(3',5'-Dichloropyridyl-2'-oxy)-phenyl]-thiollactic acid methoxycarbonylmethyl)-ester Cl Cl ~ 0 ~ OCH-C=0 SC~2C~OcH3 5.8 g (0.055 mol) of thioglycolic acid methyl ester and 5.5 g (0.055 mol) of triethylamine are added to 17.3 g (0.05 mol) of 0-[4-(3',5'-dichloropyridyl-2'-oxy)-phenyll-lactlc acid chloride in 130 ml of toluene. A~ter the exothermic reaction has subsided, the mixture is heated for 2 hours at 40C. The reaction is then cooled, the salt is filtered off, and the filtrate is concen-trated by evaporation and filtered in chloroform through a short silica gel column. Concentration by evaporation leaves 13.5 g (64.8 % of theory) of the title product in the form of oil having a refractive index n25 = 1.5580, and this product melts at 65C after recrystallisation form ether/petroleum ether.
The acid chloride required as starting material is obtained as follows: , 30 ml of thionyl chloride is added to 26.8 g (0.082 mol) of 0-[4-(3',5'-dichloropyridyl-2'-oxy)-phenyl]-lactic acid and, after the evolution of gas has subsi~ed, the mixture is heated to 50C. After two hours, the reaction mixture is concentrated in vacuo; 100 ml of toluene .
: . . .: ' . ' . . .
. : .
. .
~ ` 1 f~ 3~ 2 is added and the mixture is again concentrated by evapor-ation. There is obtained as product a dark-brown oil, which slowly commences to crystallise. The yield is 25.9 g (86.7% of theory) o 0-[4-(3',5'-dichloropyridyl-2'-oxy)-phenyl~-lactic acid chloride having a melting point of 45C.
0-[4-(3',5' Dichloropyridyl-2'-oxy)-pherlyl]-thioLartic acid-(l"-methoxycarbonyl-ethyl)-ester , .. . ,. .. _ _ _ . ____ . ~
~1 Cl ~ 0 ~ -CH-C0-SCH-COOCH
- 3 12.0 g (0~035 mol) of 0-l4-(3',5'-dichloropyridyl-2'-oxy)-phenyl]-thiolactic acid is dissolved in 50 ml of methyl ethyl ketone, and 5.5 g (0.04 mol) of potassium carbonate is added at room temperature. The temperat~re rised ~o 32C as gas is evolved. After 10 minutes, there is added 4.25 ml (0.038 mol) of 2-bromopropionic acid methyl ester. The reaction is exothermic and the tem-perature rises to 45C. The reaction mixture is filtered after 10 minutes and, after concentra~ion by evaporation and drying under high vacuum at 55C, there is obtained the pure title product having arefractive îndex n22 ~ 1.5779;
yield: 13.8 g (91.4 % of theory).
The propionthiolic acid required as starting product is produced as follows.
17.2 g (0.0496 mol) of 0-(4-(3',5'-dichloropyridyl-2'-oxy)-phenyl~-lactic acid chloride, produced as in Example 1, is added dropwise to a mixture of 8.9 g of KOH in 4.9 ml of water and 75 ml of dimethoxyethane, which has been saturated at 10-15C with H2S during vigorous stirring. As the dropwise addition is proceeding, the temperature is kept at 10C using an ice-bath. The reaction mixture is subsequently stirred for 30 minutes : ' :
.. , g ~ 43~3Z
,~
at room tempera~ure, and is then poured into 150 ml of ice/water. The pH value of the cloudy brown solution is adjusted to 1 with concentrated HCl, in the course of which there precipita~es a brown oil, which is taken up in methylene chloride. The organic phase is applied directly to a small silica gel column and is washed through with methylene chloride. The light yellow solution is concentrated by evaporation to yield a clear orange- ;
coloured oil, which crystallises on being triturated with petrolewm ether. The result is 16.8 g of a-(4-(3',5'-dichloropyridyl-2'-oxy~-phenoxy)-propionthiolic acid in the form of yellow crystals having a melting point of 85-87C.
Example 3 0-[4-(3',5'-Dichloropyridyl-2'-oxy)-phenyl~-lactic acid-(l"-ethoxycarbonylethyl) ester Cl Cl ~ _ ~ 0cH-co-o~H-cooc2Hs 12.8 g (0.05 mol) of 4-(3',5'-dichloropyridyl-2 -oxy)-phenol with 8.3 g (o.o6 mol) of potassium carbonate in 50 ml of methyl ethyl ketone is heated for one hour at boiling point. There is then added at 50C 13.2 g (0.052 mol) of 0-(2'-bromopropionyl) lactic acid ethyl ester, and the reaction mixture is stirred at 55C for 12 hours. The brown suspension is subsequently filtered, and the filtrate is concentrated in a rotary evaporator.
The brown oil is chro~atographed with petroleum ether through a small silica gel column to obtain 10.9 g (52.7 % of theory) of the title product having a refractive index nD = 1.5424.
. - ~ .
. . : ' ' . -.; , .
q ,~
The 0 (2'-bromopropionyl)-lactic acid ethyl ester of the formula CH3 i 3 Br ~ CH ~ C0- 0 - CH - COOC2H5 which is used as an intermediate product, is obtained as follows:
A mixture of 60.2 g (0.51 mol) of lactic acid ethyl ester and 51.5 g (0.51 mol) of triethylamine is added dropwise at 10-15C to 110 g (0.51 mol) of 2-bromo-propionic acid bromide in 250 ml of toluene. The whi~e suspension thus formed is filtered after 15 minutes 9 and the filtrate is concentrated by evaporation. The residue is distilled in vacuo to obtain at 78C/0.6 mm 93.6 g (72.5 % of theory) of the ester in the form of clear oil.
The esters listed in the following Table are produced in a manner analogous to that described in these Examples.
. ., - . . -, , .
' .
: ~ ....... , .. ,. ;, - , .. ..
:
`~ /v ~ 3~2 X
Ha l4~ ~--O -CH -CO -Y -Z -CO -Q
~__ No . Hal X Y Z Q Physical constants -- .. __ __~ ~ .
1 C1 C1 S C~2 O~H3 nI~5 1. 5580 2 Cl Cl S CH(CH3j OC~I3 n22 1.5779 3 Cl Cl O CH (CH3) C2H5 n22 1. 5424
yield: 13.8 g (91.4 % of theory).
The propionthiolic acid required as starting product is produced as follows.
17.2 g (0.0496 mol) of 0-(4-(3',5'-dichloropyridyl-2'-oxy)-phenyl~-lactic acid chloride, produced as in Example 1, is added dropwise to a mixture of 8.9 g of KOH in 4.9 ml of water and 75 ml of dimethoxyethane, which has been saturated at 10-15C with H2S during vigorous stirring. As the dropwise addition is proceeding, the temperature is kept at 10C using an ice-bath. The reaction mixture is subsequently stirred for 30 minutes : ' :
.. , g ~ 43~3Z
,~
at room tempera~ure, and is then poured into 150 ml of ice/water. The pH value of the cloudy brown solution is adjusted to 1 with concentrated HCl, in the course of which there precipita~es a brown oil, which is taken up in methylene chloride. The organic phase is applied directly to a small silica gel column and is washed through with methylene chloride. The light yellow solution is concentrated by evaporation to yield a clear orange- ;
coloured oil, which crystallises on being triturated with petrolewm ether. The result is 16.8 g of a-(4-(3',5'-dichloropyridyl-2'-oxy~-phenoxy)-propionthiolic acid in the form of yellow crystals having a melting point of 85-87C.
Example 3 0-[4-(3',5'-Dichloropyridyl-2'-oxy)-phenyl~-lactic acid-(l"-ethoxycarbonylethyl) ester Cl Cl ~ _ ~ 0cH-co-o~H-cooc2Hs 12.8 g (0.05 mol) of 4-(3',5'-dichloropyridyl-2 -oxy)-phenol with 8.3 g (o.o6 mol) of potassium carbonate in 50 ml of methyl ethyl ketone is heated for one hour at boiling point. There is then added at 50C 13.2 g (0.052 mol) of 0-(2'-bromopropionyl) lactic acid ethyl ester, and the reaction mixture is stirred at 55C for 12 hours. The brown suspension is subsequently filtered, and the filtrate is concentrated in a rotary evaporator.
The brown oil is chro~atographed with petroleum ether through a small silica gel column to obtain 10.9 g (52.7 % of theory) of the title product having a refractive index nD = 1.5424.
. - ~ .
. . : ' ' . -.; , .
q ,~
The 0 (2'-bromopropionyl)-lactic acid ethyl ester of the formula CH3 i 3 Br ~ CH ~ C0- 0 - CH - COOC2H5 which is used as an intermediate product, is obtained as follows:
A mixture of 60.2 g (0.51 mol) of lactic acid ethyl ester and 51.5 g (0.51 mol) of triethylamine is added dropwise at 10-15C to 110 g (0.51 mol) of 2-bromo-propionic acid bromide in 250 ml of toluene. The whi~e suspension thus formed is filtered after 15 minutes 9 and the filtrate is concentrated by evaporation. The residue is distilled in vacuo to obtain at 78C/0.6 mm 93.6 g (72.5 % of theory) of the ester in the form of clear oil.
The esters listed in the following Table are produced in a manner analogous to that described in these Examples.
. ., - . . -, , .
' .
: ~ ....... , .. ,. ;, - , .. ..
:
`~ /v ~ 3~2 X
Ha l4~ ~--O -CH -CO -Y -Z -CO -Q
~__ No . Hal X Y Z Q Physical constants -- .. __ __~ ~ .
1 C1 C1 S C~2 O~H3 nI~5 1. 5580 2 Cl Cl S CH(CH3j OC~I3 n22 1.5779 3 Cl Cl O CH (CH3) C2H5 n22 1. 5424
4 Cl Cl S CH(CH3) NHC2H5 m.p. 113-14C
Cl Cl O CH (t::H3) 2H5 6 Cl Cl S CH2 NH2 m . p ~98 100C
7 Cl Cl C~2 ~H2 m-p. 154 59C
9 Cl Cl S G2H4 OCH3 11 Cl Cl O 2 O~I3 nD 1.5489 13 C 1 Cl S CH2 OEI
14 Cl Cl O CHCN C2H5, 2 lS Cl Cl O C~ICOOC~H OC2H5 n~ l o 5339 16 C l C l S CHCOOC2H j OC2~5 n~2 1 . 5 4 61 17 Cl Cl S C~ICN 3C2H5 nD2 1. 5612 18 Cl Cl O CHCOCH3 ~CH3 19 Cl Cl S CHCOCH3 ~CH3 .
Cl H S C~2 ~CH3 21 Cl H C;H2 C~3 22 1 5598 2 2 Cl Cl S CHCOCH3OC2H5 nD2 23 Cl Cl S 2 4 C2HS n~? 1. 5580 24 Cl Cl O CHCOC~I3OC2EI5 nD 1. 5253 Cl Cl S C2H4 NH;~ m.p. 109-10 C
--__ _ ~ ~
:
. ~ . -:, . . .
.
~ , . . ,: - - . .. . .
- ~ - .
3~3Z
~ ,1 ,~
The novel active substances of the formula I are stable compounds which are soluble in customary organic solvents, such as alcohols, ethers, ketones, dimethyl-formamide, dimethyl sulfoxide, and so forth.
The invention relates also to compos-itions having a herbicidal and plant-growth-regulating action, which contain a novel active substance of the formula I, and to processes for the pre-emergence and post--emergence combating of weeds, and for the inhibition of the growth of monocotyledonous and dicotyledonous plants, particularly of grasses, cereals and soya bean plants, and of side shoots of tobacco plants.
The compositions according to the invention can be fonmulated in the customary manner.
The compositions according to the invention are produced in a manner known per se by the intimate mixing and grinding of active substances of the formula I with suitable carriers~ optionally with the addition of dispersing agents or solvents which are inert to the active substances. The active substances can be obtained and used in the following ~orms:
solid ~re~rations: dusts, scatt2ring agents, granules tcoated granules, impregnated granules and homogeneous granules);
water-dispersible concentrates_of active substance:
wettable powders, pastes and emulsions;
liquid preparat ons: solutions.
The concentration of active substance in the compo-sitions according to the invention is 1 to 80 per cent by weight, and when being applied the compositions can if necessary contain the active substances also at a lower concentration, such as about 0.05 to 1 per cent.
.
. :
.
: ' , i43B~
,~
Other bioci.dal active substances or compositions can be added to the compositions according to the invention.
In order to widen their sphere of action, the novel compositions can thus contain, in addition to the stated compounds of the formula I, for example insecticides, fungicides, bactericides, fungistatics, bacteriostatics, nematocides or further herbicides.
Some examples of solid and li~uid preparations are described in the following in order to illustrate the production of compositions according to the invention.
Wettable powder The following constituents are used to produce a) a 50% wettable powder, b) a 25% wettable powder, and c) a 10% wettable powder:
a) 50 parts of active substance, parts of sodium dibutyl naphthyl sulfonate, 3 parts of naphthalenesulfonic acid/phenol-sulfonic acid/formaldehyde condensate (3:2:1), 29 parts of kaolin, and 22 parts of Champagne chalk;
b) 25 parts of active substance, S parts of the sodium salt of oleylmethyl tauride, 2.5 parts of a naphthalenesulfonic acid/
formaldehyde condensate, 0.5 part of carboxymethylcellulose, parts of neutral potassium aluminium silicate, and 62 parts of kaolin; and c) 10 parts of active substance, .
3 parts of a mixture of the sodium salts of saturated fatty alcohols, . , . . ~ .. .. _,.. . . . .
. . . .
. ~ . . .
~ ' . , .
., .
.' , ,' '-, ' ' ' 3i~Z
,~
parts of a naphthalenesulfonic acid/
ormaldehyde condensate, and 82 parts of kaolin.
The given active substance is absorbed onto the appro-priate carriers (kaolin and chalk), and the material is subsequently mixed and ground with the remaining con-stituents. Wettable powders having excellent wetting and suspension properties are obtained. It is possible to obtain from wettable powders of this kind, by dilution with water, suspensions having an active-substance concentration which is suitable for combating weeds in crops of cultiva~ed plants.
Paste The following materials are used to produce a 45% paste:
4S parts of one of the active substances of the formula I, parts of sodium aluminium silicate, 14 parts of cetyl polyglycol ether having 8 mols of ethylene oxide, 1 part of oleyl polyglycol ether having 5 mols of ethylene oxide, 2 parts of spindle oil, parts of polyethylene glycol, and 23 parts of water.
The active substance is intimately mixed and ground with the additives in apparatus suitable for the purpose.
There is obtained a paste from which can be produced, by dilution with water, suspensions of any desired concentration.
}~uls~on C~n cen C =a t~
The following constituents ar~ mixed together to . .
.
.. . .
. . .
. .. . . .
- . ~
.' ' . ' . ~ . :
~ ` ' ' ': :
/~ L3~32 produce a 25% emulsiun concentrate:
~5 parts of one of the active substances of the formula I, parts of a mi~ture of nonylphenolpolyoxy-ethylene and calcium dodecylbenzene sulfate~
parts of cyclohexanone, and parts of xylene.
This concentrate can be diluted with water to give emulsions of suitable concentration, for example 0.1 to 10%. Emulsions of this kind are suitable for combating weeds in crops of cultivated plants.
Compositions according to the invention, which contain as active substance at least one ccmpound of the formula I, are suitable in particular for selectively combating monocotyledonous wild grasses, by pre-emergence and especially post-emergence application, in crops of cultivated plants, or example in crops of soya bean, cotton, sugar beet, wheat and other varieties o~ cereals.
The following test methods serve to verify the suitability of the novel active substances of the formula I as herbicides (pre- and post-emergence), and to prove the superiority of them over known active substances of similar structure.
Pre-emer~ence herbicidal action (inhibition of germination) Im~ediately after sowing the test plants in seed trays in a greenhouse, the surace o the soil is treated with an aqueous dispersion of the active substance, which has been prepared from a 25% emulsion concentrate, and from a 25% wettable powder con~aining active substances which cannot be produced as emulsion concentrates owing to inadequate solubility. Four di~ferent concentration .43~
,~
series are used, corresponding to 4, 2, 1 and 0.5 kg of active substance per hectare. The sPed trays are left in the greenhouse at 22-25C with 50-70% relative humidity, and the test is evaluated after 3 weeks, with the resuLts being assessed according to the following scale of ratings:
1 = plants have not germinated or have fully died off, 2-3 - very intense action, 4-6 = moderate action, 7-8 - slight action, 9 = no action (as in the case of untreated control plants).
O-(Pyridyloxy-phenoxy)-laetic acid esters according to the invention are compared in this test with the following structurally similar compounds:
Cl c~3 Cl ~ o ~ o-c~-COSC~2-COOC~l3 0-[4-(2',4'-dichlorophe~oxy)-phenyl-thio-lactic acid (methoxycarbonylmethyl) ester~ known from the German Offenlegungsschrift No. 2,628,384, Example 3;
Cl~ 3OC~-~OOC~-COOC~}15 0-~4-~2',4'-dichlorophenoxy)-phenyl-lactic acid-(ethoxy-carbonylethyl) ester, known from the German Offenlegungs schrift No. 2,628,384, Example 23.
The following plants were tested: barley and cotton, as well as the weeds Avena a~ua, Alopecurus myosuroides, Rottboellia exaltata and Digitaria sanguinalis.
. , : .
' ' : ~ . : ~
The results are su~narlsed in the Table given below. :
___ ~ , . ~_ ~ ~ 1 ~ Ot Cr~
_~ ~ 1 ~ ~r ~ 1 : '' _ __ _ _ cn ~ ~ ~ ~ ~ ~ ~
~r a~ ~ ~r ~ ,1 ~ e: a~ o~ 0 ~D f'~ ~1 a~ 1 ~o ~ : -~r ~ ~ l ~ ~ ~ cr~ 1 . :
.
,~ ~1 ~ ~ ~ 1` ~ _1 ~1 ~ a~ 1 ~ ~r ~ 1 ___ .
Cl Cl O CH (t::H3) 2H5 6 Cl Cl S CH2 NH2 m . p ~98 100C
7 Cl Cl C~2 ~H2 m-p. 154 59C
9 Cl Cl S G2H4 OCH3 11 Cl Cl O 2 O~I3 nD 1.5489 13 C 1 Cl S CH2 OEI
14 Cl Cl O CHCN C2H5, 2 lS Cl Cl O C~ICOOC~H OC2H5 n~ l o 5339 16 C l C l S CHCOOC2H j OC2~5 n~2 1 . 5 4 61 17 Cl Cl S C~ICN 3C2H5 nD2 1. 5612 18 Cl Cl O CHCOCH3 ~CH3 19 Cl Cl S CHCOCH3 ~CH3 .
Cl H S C~2 ~CH3 21 Cl H C;H2 C~3 22 1 5598 2 2 Cl Cl S CHCOCH3OC2H5 nD2 23 Cl Cl S 2 4 C2HS n~? 1. 5580 24 Cl Cl O CHCOC~I3OC2EI5 nD 1. 5253 Cl Cl S C2H4 NH;~ m.p. 109-10 C
--__ _ ~ ~
:
. ~ . -:, . . .
.
~ , . . ,: - - . .. . .
- ~ - .
3~3Z
~ ,1 ,~
The novel active substances of the formula I are stable compounds which are soluble in customary organic solvents, such as alcohols, ethers, ketones, dimethyl-formamide, dimethyl sulfoxide, and so forth.
The invention relates also to compos-itions having a herbicidal and plant-growth-regulating action, which contain a novel active substance of the formula I, and to processes for the pre-emergence and post--emergence combating of weeds, and for the inhibition of the growth of monocotyledonous and dicotyledonous plants, particularly of grasses, cereals and soya bean plants, and of side shoots of tobacco plants.
The compositions according to the invention can be fonmulated in the customary manner.
The compositions according to the invention are produced in a manner known per se by the intimate mixing and grinding of active substances of the formula I with suitable carriers~ optionally with the addition of dispersing agents or solvents which are inert to the active substances. The active substances can be obtained and used in the following ~orms:
solid ~re~rations: dusts, scatt2ring agents, granules tcoated granules, impregnated granules and homogeneous granules);
water-dispersible concentrates_of active substance:
wettable powders, pastes and emulsions;
liquid preparat ons: solutions.
The concentration of active substance in the compo-sitions according to the invention is 1 to 80 per cent by weight, and when being applied the compositions can if necessary contain the active substances also at a lower concentration, such as about 0.05 to 1 per cent.
.
. :
.
: ' , i43B~
,~
Other bioci.dal active substances or compositions can be added to the compositions according to the invention.
In order to widen their sphere of action, the novel compositions can thus contain, in addition to the stated compounds of the formula I, for example insecticides, fungicides, bactericides, fungistatics, bacteriostatics, nematocides or further herbicides.
Some examples of solid and li~uid preparations are described in the following in order to illustrate the production of compositions according to the invention.
Wettable powder The following constituents are used to produce a) a 50% wettable powder, b) a 25% wettable powder, and c) a 10% wettable powder:
a) 50 parts of active substance, parts of sodium dibutyl naphthyl sulfonate, 3 parts of naphthalenesulfonic acid/phenol-sulfonic acid/formaldehyde condensate (3:2:1), 29 parts of kaolin, and 22 parts of Champagne chalk;
b) 25 parts of active substance, S parts of the sodium salt of oleylmethyl tauride, 2.5 parts of a naphthalenesulfonic acid/
formaldehyde condensate, 0.5 part of carboxymethylcellulose, parts of neutral potassium aluminium silicate, and 62 parts of kaolin; and c) 10 parts of active substance, .
3 parts of a mixture of the sodium salts of saturated fatty alcohols, . , . . ~ .. .. _,.. . . . .
. . . .
. ~ . . .
~ ' . , .
., .
.' , ,' '-, ' ' ' 3i~Z
,~
parts of a naphthalenesulfonic acid/
ormaldehyde condensate, and 82 parts of kaolin.
The given active substance is absorbed onto the appro-priate carriers (kaolin and chalk), and the material is subsequently mixed and ground with the remaining con-stituents. Wettable powders having excellent wetting and suspension properties are obtained. It is possible to obtain from wettable powders of this kind, by dilution with water, suspensions having an active-substance concentration which is suitable for combating weeds in crops of cultiva~ed plants.
Paste The following materials are used to produce a 45% paste:
4S parts of one of the active substances of the formula I, parts of sodium aluminium silicate, 14 parts of cetyl polyglycol ether having 8 mols of ethylene oxide, 1 part of oleyl polyglycol ether having 5 mols of ethylene oxide, 2 parts of spindle oil, parts of polyethylene glycol, and 23 parts of water.
The active substance is intimately mixed and ground with the additives in apparatus suitable for the purpose.
There is obtained a paste from which can be produced, by dilution with water, suspensions of any desired concentration.
}~uls~on C~n cen C =a t~
The following constituents ar~ mixed together to . .
.
.. . .
. . .
. .. . . .
- . ~
.' ' . ' . ~ . :
~ ` ' ' ': :
/~ L3~32 produce a 25% emulsiun concentrate:
~5 parts of one of the active substances of the formula I, parts of a mi~ture of nonylphenolpolyoxy-ethylene and calcium dodecylbenzene sulfate~
parts of cyclohexanone, and parts of xylene.
This concentrate can be diluted with water to give emulsions of suitable concentration, for example 0.1 to 10%. Emulsions of this kind are suitable for combating weeds in crops of cultivated plants.
Compositions according to the invention, which contain as active substance at least one ccmpound of the formula I, are suitable in particular for selectively combating monocotyledonous wild grasses, by pre-emergence and especially post-emergence application, in crops of cultivated plants, or example in crops of soya bean, cotton, sugar beet, wheat and other varieties o~ cereals.
The following test methods serve to verify the suitability of the novel active substances of the formula I as herbicides (pre- and post-emergence), and to prove the superiority of them over known active substances of similar structure.
Pre-emer~ence herbicidal action (inhibition of germination) Im~ediately after sowing the test plants in seed trays in a greenhouse, the surace o the soil is treated with an aqueous dispersion of the active substance, which has been prepared from a 25% emulsion concentrate, and from a 25% wettable powder con~aining active substances which cannot be produced as emulsion concentrates owing to inadequate solubility. Four di~ferent concentration .43~
,~
series are used, corresponding to 4, 2, 1 and 0.5 kg of active substance per hectare. The sPed trays are left in the greenhouse at 22-25C with 50-70% relative humidity, and the test is evaluated after 3 weeks, with the resuLts being assessed according to the following scale of ratings:
1 = plants have not germinated or have fully died off, 2-3 - very intense action, 4-6 = moderate action, 7-8 - slight action, 9 = no action (as in the case of untreated control plants).
O-(Pyridyloxy-phenoxy)-laetic acid esters according to the invention are compared in this test with the following structurally similar compounds:
Cl c~3 Cl ~ o ~ o-c~-COSC~2-COOC~l3 0-[4-(2',4'-dichlorophe~oxy)-phenyl-thio-lactic acid (methoxycarbonylmethyl) ester~ known from the German Offenlegungsschrift No. 2,628,384, Example 3;
Cl~ 3OC~-~OOC~-COOC~}15 0-~4-~2',4'-dichlorophenoxy)-phenyl-lactic acid-(ethoxy-carbonylethyl) ester, known from the German Offenlegungs schrift No. 2,628,384, Example 23.
The following plants were tested: barley and cotton, as well as the weeds Avena a~ua, Alopecurus myosuroides, Rottboellia exaltata and Digitaria sanguinalis.
. , : .
' ' : ~ . : ~
The results are su~narlsed in the Table given below. :
___ ~ , . ~_ ~ ~ 1 ~ Ot Cr~
_~ ~ 1 ~ ~r ~ 1 : '' _ __ _ _ cn ~ ~ ~ ~ ~ ~ ~
~r a~ ~ ~r ~ ,1 ~ e: a~ o~ 0 ~D f'~ ~1 a~ 1 ~o ~ : -~r ~ ~ l ~ ~ ~ cr~ 1 . :
.
,~ ~1 ~ ~ ~ 1` ~ _1 ~1 ~ a~ 1 ~ ~r ~ 1 ___ .
5~ ~ ~ ~ ~ ~
.. 7 er ,~ ~ ~ .
a~ ~r a~ 1 . - - ,, c~ l ~ ~
~r ~ ~r ~ 1 - - - - -- - -:~
-l ~l ~ l ~ ~ ~ ~ _ _I
~n a~~n ~rl ~ ~ rl .~ rl ~ ~
~ O ~d ~ ~ O ~ ~ :', 5~ ~ ~ rl 5~ ~ 1 ~d ~ ~ ~ , .
X bO ~ ~ O ~ .
O ~.C ~ O ~0.~ ~ , ~
zi ~ ~ ~ ,1 æ ~ ~ ~O ,, S~ ~ ~ 5~ J~ i., .
a ~ ~ ~ ~ ~ ~ ~ ~ . ~
~o ~ ~ ~ 0~ O,a~ ~o ~ ~ : :.
,~ v ~ rl ~ ~ ~ ~ v ~
5, v ~ o v ~4 ~ ~ s~ v a~ o v bO ":
O ~ ~_1 0 ~ O C~ ~ ~ O ~ ~ O rl c~,~ ~ 4 ~C ~ a w ~s ~ ~ ~:
., ~
.. .
t~ . ` . : -- --~ --~.. _ ~_ .. ___.. ~.. _ __~_ ~ _, _,,_ _ _ - ~ ' , . ' ':' : . , ' '' . . ' ., ' ' '' . . , , ' ' , ' . .
' , ' ~ ' , . ~ ' :
~ 3~32 Post-emer ence herbicidal action ~contact herbicide) _ g _ _ _ _ A considerable number (at Least 7) of weeds and of cultivated plants, both monocotyledonous and dicotyledonous, are sprayed after emergence (in the 4- to 6-leaf stage) with an aqueous active~substance dispersion in dosage amounts o 1, 1/2, 1/4 and 1/8 kg of active substance per hectare, and they are then kept at 24 26C with 45-60% relative humidity. The test is evaluated lS days after treatment, and the results are assessed according to the same scale of ratings as used in the pre-emergence ~est.
The following plants are tested: wheat, soya bean and sugar beet~ as weLl as the weeds Avena fatua, Lolium perenne, Alopecurus myosuroides and Setaria italica The results are summarised in the Table which follows.
, =~......................... . . . ;
, ~' ' , , /~ 3~
.~ ,~
..
u~O ~
~ ,, ~ ~ ,, ,, ,, ~
__ ~ I U~
~ O a~ 1 a~ ~
~1 ~ l ~1 ~ ~ ~ O~ ~
_ _ _ __ r~ O a~ ~ O a~
~ ~ ~ c~
_ ~. _ _ _ _ . .' . u~ I . a~ ~1 ~o o ~ o ~ ~ ~1 ~ ~ ~ ~ 1 _ _ _ ~ a~ I ~1 ~1 ~ ~ ~ ~
O r a~ ~ O ~ , . . -- . - :-O ~ ~ ~ , ~, ,~ ~ 1 _1 ~ 1 : ~, - - - - - -. ~ a~ I .
O " O
,~ r~ _1 ~ , -- ~ - ~
) ~ 1 ~I Q ~ i.
r~l ao a~ 1 ~1 ~1 _I ~ ~ ~ ~I ~ l _ . _ __ - O' '~,:
~r:l . ~c) ~ ~
h ~ O
~ O s.) ~, ~ ~
~ 5 Ei ~-l ~ C ~. ~
æ ~ 5. o ~ o~l~ s~
~ ~ ~ ~ ~ ~ ~ U ~ P
o ~ ~ u ~ o ~ ~ ~
8.~c ~ 3 1 83~ , o ~
..
.
-, ,~ , . . . . . .
. ..
.
. , , , ~, . ,
.. 7 er ,~ ~ ~ .
a~ ~r a~ 1 . - - ,, c~ l ~ ~
~r ~ ~r ~ 1 - - - - -- - -:~
-l ~l ~ l ~ ~ ~ ~ _ _I
~n a~~n ~rl ~ ~ rl .~ rl ~ ~
~ O ~d ~ ~ O ~ ~ :', 5~ ~ ~ rl 5~ ~ 1 ~d ~ ~ ~ , .
X bO ~ ~ O ~ .
O ~.C ~ O ~0.~ ~ , ~
zi ~ ~ ~ ,1 æ ~ ~ ~O ,, S~ ~ ~ 5~ J~ i., .
a ~ ~ ~ ~ ~ ~ ~ ~ . ~
~o ~ ~ ~ 0~ O,a~ ~o ~ ~ : :.
,~ v ~ rl ~ ~ ~ ~ v ~
5, v ~ o v ~4 ~ ~ s~ v a~ o v bO ":
O ~ ~_1 0 ~ O C~ ~ ~ O ~ ~ O rl c~,~ ~ 4 ~C ~ a w ~s ~ ~ ~:
., ~
.. .
t~ . ` . : -- --~ --~.. _ ~_ .. ___.. ~.. _ __~_ ~ _, _,,_ _ _ - ~ ' , . ' ':' : . , ' '' . . ' ., ' ' '' . . , , ' ' , ' . .
' , ' ~ ' , . ~ ' :
~ 3~32 Post-emer ence herbicidal action ~contact herbicide) _ g _ _ _ _ A considerable number (at Least 7) of weeds and of cultivated plants, both monocotyledonous and dicotyledonous, are sprayed after emergence (in the 4- to 6-leaf stage) with an aqueous active~substance dispersion in dosage amounts o 1, 1/2, 1/4 and 1/8 kg of active substance per hectare, and they are then kept at 24 26C with 45-60% relative humidity. The test is evaluated lS days after treatment, and the results are assessed according to the same scale of ratings as used in the pre-emergence ~est.
The following plants are tested: wheat, soya bean and sugar beet~ as weLl as the weeds Avena fatua, Lolium perenne, Alopecurus myosuroides and Setaria italica The results are summarised in the Table which follows.
, =~......................... . . . ;
, ~' ' , , /~ 3~
.~ ,~
..
u~O ~
~ ,, ~ ~ ,, ,, ,, ~
__ ~ I U~
~ O a~ 1 a~ ~
~1 ~ l ~1 ~ ~ ~ O~ ~
_ _ _ __ r~ O a~ ~ O a~
~ ~ ~ c~
_ ~. _ _ _ _ . .' . u~ I . a~ ~1 ~o o ~ o ~ ~ ~1 ~ ~ ~ ~ 1 _ _ _ ~ a~ I ~1 ~1 ~ ~ ~ ~
O r a~ ~ O ~ , . . -- . - :-O ~ ~ ~ , ~, ,~ ~ 1 _1 ~ 1 : ~, - - - - - -. ~ a~ I .
O " O
,~ r~ _1 ~ , -- ~ - ~
) ~ 1 ~I Q ~ i.
r~l ao a~ 1 ~1 ~1 _I ~ ~ ~ ~I ~ l _ . _ __ - O' '~,:
~r:l . ~c) ~ ~
h ~ O
~ O s.) ~, ~ ~
~ 5 Ei ~-l ~ C ~. ~
æ ~ 5. o ~ o~l~ s~
~ ~ ~ ~ ~ ~ ~ U ~ P
o ~ ~ u ~ o ~ ~ ~
8.~c ~ 3 1 83~ , o ~
..
.
-, ,~ , . . . . . .
. ..
.
. , , , ~, . ,
Claims (6)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. O-(Pyridyloxy-phenyl)-lactic acid ester of the formula I
(I) in which "Hal" is a halogen atom, X is hydrogen or a halogen atom, Y is an oxygen or sulfur atom, Z is a C1-C4-alkylene group which is unsubstituted or sub-stituted by methyl, ethyl, cyano, methylcarbonyl or by a group -COQ, and Q is a group -OR1, -SR2 or -NR3R4, wherein R1, R2, R3 and R4 independently of one another are each hydrogen or C1 to C4-alkyl.
(I) in which "Hal" is a halogen atom, X is hydrogen or a halogen atom, Y is an oxygen or sulfur atom, Z is a C1-C4-alkylene group which is unsubstituted or sub-stituted by methyl, ethyl, cyano, methylcarbonyl or by a group -COQ, and Q is a group -OR1, -SR2 or -NR3R4, wherein R1, R2, R3 and R4 independently of one another are each hydrogen or C1 to C4-alkyl.
2. O-[4-(3',5'-Dichloropyridyl-2'-oxy)-phenyl]-thiolactic acid-(methoxycarbonylmethyl) ester.
3. O-[4-(3',5'-Dichloropyridyl-2'-oxy)-phenyl]-thiolactic acid-(methoxycarbonylethyl) ester.
4. A process for producing an O-(pyridyloxy-phenyl)-lactic acid ester of formula I as defined in claim 1, which process com-prises reacting in a manner known per se, according to the reaction patterns given below, (a) an appropriately substituted 4-(5'-halogenopyridyl-2'-oxy)-phenol, in the presence of a base, with a 2-halogenopropionic acid deriva-tive of the formula wherein "Hal", Q, X, Y and Z have the meanings defined in claim 1;
(b) reacting an O-[4-(5,-halogenopyridyl-2'-oxy)-phenyl]-lactic acid or -thiolactic acid, in the presence of a base, with a halogeno-carboxylic acid ester of the formula Hal - Z - CO - Q
wherein "Hal", Q, X, Y and Z have the meanings defined in claim 1;
or (c) reacting an acid halide of an O-[4-(5'-halogenopyridyl-2'-oxy)-phenyl]-lactic acid, in the presence of a base, with an ester of a hydroxycarboxylic acid or mercapto-carboxylic acid of the formula HY - Z - CO - Q
wherein "Hal", Q, X, Y and Z have the meanings defined in claim 1.
(b) reacting an O-[4-(5,-halogenopyridyl-2'-oxy)-phenyl]-lactic acid or -thiolactic acid, in the presence of a base, with a halogeno-carboxylic acid ester of the formula Hal - Z - CO - Q
wherein "Hal", Q, X, Y and Z have the meanings defined in claim 1;
or (c) reacting an acid halide of an O-[4-(5'-halogenopyridyl-2'-oxy)-phenyl]-lactic acid, in the presence of a base, with an ester of a hydroxycarboxylic acid or mercapto-carboxylic acid of the formula HY - Z - CO - Q
wherein "Hal", Q, X, Y and Z have the meanings defined in claim 1.
5. A method for combating weeds, which comprises treating an area where weeds occur with an effective amount of an O-(pyridyl-oxy-phenyl)-lactic acid ester of formula I as defined in claim 1 or of a composition containing such an ester of formula I.
6. A method for regulating plant growth, which comprises treating plants, the growth of which has to be influenced, with an effective amount of an O-(pyridyloxy-phenyl)-lactic acid ester of formula I as defined in claim 1 or of a composition containing such an ester of formula I.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH7242/78-8 | 1978-07-03 | ||
| CH724278 | 1978-07-03 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1114382A true CA1114382A (en) | 1981-12-15 |
Family
ID=4322076
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA330,939A Expired CA1114382A (en) | 1978-07-03 | 1979-06-29 | Esters of 0-(pyridyloxy-phenyl)-lactic acids |
Country Status (19)
| Country | Link |
|---|---|
| EP (1) | EP0008624B1 (en) |
| JP (1) | JPS559093A (en) |
| KR (1) | KR840002123B1 (en) |
| AR (1) | AR225613A1 (en) |
| AT (1) | ATE721T1 (en) |
| AU (1) | AU535738B2 (en) |
| BR (1) | BR7904168A (en) |
| CA (1) | CA1114382A (en) |
| CS (1) | CS204960B2 (en) |
| DD (1) | DD151037A5 (en) |
| DE (1) | DE2962189D1 (en) |
| ES (1) | ES482110A1 (en) |
| HU (1) | HU182939B (en) |
| IL (1) | IL57709A (en) |
| MX (1) | MX5681E (en) |
| NZ (1) | NZ190896A (en) |
| PH (1) | PH15718A (en) |
| TR (1) | TR20632A (en) |
| ZA (1) | ZA793282B (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3034845A1 (en) * | 1980-09-16 | 1982-05-06 | Hoechst Ag, 6000 Frankfurt | INCREASED CARBOHYDRATE STORAGE IN PLANTS BY SUBSTITUTED PHENOXYALKANIC ACID DERIVATIVES |
| US4505743A (en) * | 1981-12-31 | 1985-03-19 | Ciba-Geigy Corporation | α-[4-(3-Fluoro-5'-halopyridyl-2'-oxy)-phenoxy]-propionic acid derivatives having herbicidal activity |
| US4518416A (en) * | 1982-06-04 | 1985-05-21 | Bayer Aktiengesellschaft | Certain trimethyl silyl-lower-alkyl esters of pyridyloxy-phenoxy-lower alkanoic acids, compositions containing same and herbicidal method of use |
| EP0200677B1 (en) * | 1985-04-01 | 1991-04-03 | Ciba-Geigy Ag | 3-fluoropyridyl-2-oxy-phenoxy derivatives with a herbicidal activity |
| JPS61249954A (en) * | 1985-04-26 | 1986-11-07 | Aguro Kanesho Kk | Propionic acid derivative |
| JPS62273954A (en) * | 1986-05-21 | 1987-11-28 | Aguro Kanesho Kk | Hydroxyacetic acid amide derivative |
| KR940005924B1 (en) | 1989-01-12 | 1994-06-24 | 가네보가부시끼가이샤 | Composite filament yarn and process and spinneret manufacturing the same |
| AU6540490A (en) * | 1989-10-05 | 1991-04-28 | Hoechst Aktiengesellschaft | Herbicidal, heterocyclically substituted phenoxyalkane carboxylic acid derivatives and process for preparing them |
| JP2836978B2 (en) * | 1990-01-18 | 1998-12-14 | 鐘紡 株式会社 | Composite elastic yarn |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DK154074C (en) * | 1974-10-17 | 1989-02-27 | Ishihara Sangyo Kaisha | ALFA- (4- (5 OR 3.5 SUBSTITUTED PYRIDYL-2-OXY) -PHENOXY) -ALKANE CARBOXYLIC ACIDS OR DERIVATIVES THEREOF USED AS HERBICIDES, HERBICIDES AND PROCEDURES |
| CH620339A5 (en) * | 1976-03-05 | 1980-11-28 | Ciba Geigy Ag | |
| JPS52131540A (en) * | 1976-04-14 | 1977-11-04 | Ishihara Sangyo Kaisha Ltd | Phenoxyvaleric acid derivatives and herbicides therefrom |
| DE2628384C2 (en) * | 1976-06-24 | 1984-09-27 | Hoechst Ag, 6230 Frankfurt | 2- (4-Phenoxyphenoxy) - or 2- (4-Benzylphenoxy) propionic acid derivatives, process for their preparation and their use as plant treatment agents |
| US4133675A (en) * | 1976-07-23 | 1979-01-09 | Ciba-Geigy Corporation | Pyridyloxy-phenoxy-alkanecarboxylic acid derivatives which are effective as herbicides and as agents regulating plant growth |
| TR19824A (en) * | 1977-07-21 | 1980-01-24 | Ishihara Sangyo Kaisha | TRILOROMETHYLPIRIDOXIFENOXYPROPIONIC AS TUEREVLER AND HERBISIDES THAT CONTAIN THEM |
| CA1247625A (en) * | 1977-07-22 | 1988-12-28 | Howard Johnston | Trifluoromethyl pyridinyloxyphenoxy propanoic acids and propanols and derivatives thereof and methods of herbicidal use |
-
1979
- 1979-06-29 DE DE7979102185T patent/DE2962189D1/en not_active Expired
- 1979-06-29 CA CA330,939A patent/CA1114382A/en not_active Expired
- 1979-06-29 EP EP79102185A patent/EP0008624B1/en not_active Expired
- 1979-06-29 AT AT79102185T patent/ATE721T1/en not_active IP Right Cessation
- 1979-06-29 DD DD79213996A patent/DD151037A5/en unknown
- 1979-07-02 PH PH22731A patent/PH15718A/en unknown
- 1979-07-02 IL IL57709A patent/IL57709A/en unknown
- 1979-07-02 ZA ZA793282A patent/ZA793282B/en unknown
- 1979-07-02 BR BR7904168A patent/BR7904168A/en unknown
- 1979-07-02 HU HU79CI1946A patent/HU182939B/en not_active IP Right Cessation
- 1979-07-02 NZ NZ190896A patent/NZ190896A/en unknown
- 1979-07-02 CS CS794625A patent/CS204960B2/en unknown
- 1979-07-02 AU AU48583/79A patent/AU535738B2/en not_active Ceased
- 1979-07-02 ES ES482110A patent/ES482110A1/en not_active Expired
- 1979-07-02 AR AR277149A patent/AR225613A1/en active
- 1979-07-03 KR KR7902204A patent/KR840002123B1/en active
- 1979-07-03 JP JP8436879A patent/JPS559093A/en active Granted
- 1979-07-03 MX MX798149U patent/MX5681E/en unknown
- 1979-07-03 TR TR20632A patent/TR20632A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| AU4858379A (en) | 1980-01-10 |
| NZ190896A (en) | 1982-03-09 |
| ES482110A1 (en) | 1980-04-01 |
| ZA793282B (en) | 1980-08-27 |
| DD151037A5 (en) | 1981-09-30 |
| DE2962189D1 (en) | 1982-03-25 |
| KR840002123B1 (en) | 1984-11-19 |
| BR7904168A (en) | 1980-03-25 |
| JPS559093A (en) | 1980-01-22 |
| AU535738B2 (en) | 1984-04-05 |
| AR225613A1 (en) | 1982-04-15 |
| ATE721T1 (en) | 1982-03-15 |
| EP0008624A1 (en) | 1980-03-19 |
| HU182939B (en) | 1984-03-28 |
| CS204960B2 (en) | 1981-04-30 |
| TR20632A (en) | 1982-03-12 |
| MX5681E (en) | 1983-12-08 |
| JPH0122266B2 (en) | 1989-04-25 |
| EP0008624B1 (en) | 1982-02-24 |
| PH15718A (en) | 1983-03-18 |
| IL57709A (en) | 1982-07-30 |
| KR830001218A (en) | 1983-04-29 |
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Legal Events
| Date | Code | Title | Description |
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| MKEX | Expiry |