DE2758002A1 - Optically active phenoxy-propionic acid derivs. - which are more powerful herbicides than corresp. racemate - Google Patents
Optically active phenoxy-propionic acid derivs. - which are more powerful herbicides than corresp. racemateInfo
- Publication number
- DE2758002A1 DE2758002A1 DE19772758002 DE2758002A DE2758002A1 DE 2758002 A1 DE2758002 A1 DE 2758002A1 DE 19772758002 DE19772758002 DE 19772758002 DE 2758002 A DE2758002 A DE 2758002A DE 2758002 A1 DE2758002 A1 DE 2758002A1
- Authority
- DE
- Germany
- Prior art keywords
- alkyl
- phenyl
- formula
- phenoxy
- alkoxy
- 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.)
- Withdrawn
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- C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
- C07D263/52—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings condensed with carbocyclic rings or ring systems
- C07D263/54—Benzoxazoles; Hydrogenated benzoxazoles
- C07D263/58—Benzoxazoles; Hydrogenated benzoxazoles 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 in position 2
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- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/36—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids
- A01N37/38—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids having at least one oxygen or sulfur atom attached to an aromatic ring system
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- A01N43/06—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings
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- A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
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- A01N47/18—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, directly attached to a heterocyclic or cycloaliphatic ring
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- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
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- C07C235/18—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton being acyclic and saturated having at least one of the singly-bound oxygen atoms further bound to a carbon atom of a six-membered aromatic ring, e.g. phenoxyacetamides
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Abstract
Description
Es ist bekannt, daß viele Naturstoffe mit biologischer Wirksamkeit infolge des Vorhandenseins eines oder mehrerer asymmetrischer Kohlenstoffatome optisch aktiv sind, d.h. die Ebene des polarisierten Lichtes nach rechts {+) oder links (-) drehen. Sehr oft weisen diese Verbindungen eine höhere *) auf als entsprechende synthetisch gewonnene, optisch inaktive Verbindungen. Ähnliches gilt für manche synthetisch hergestellte Wirkstoffe wie Pharmazeutika oder Pflanzenschutzmittel mit asymmetrischen C-Atomen, die gewöhnlich bei der Synthese als optisch inaktive Racemate, d.h. Gemische aus gleichen Anteilen der rechts- und der linksdrehenden Enantiomeren, anfallen. Auch hier wird bei der Isomerentrennung nicht selten gefunden, daß die Wirksamkeit eines der beiden Enantiomeren höher ist als die des Racemats. Ob die links (-)- oder die rechts(+)-drehende Form die jeweils aktive ist und ob überhaupt ein Zusammenhang zwischen Wirkung und optischer Aktivität besteht, läßt sich jedoch nicht vorhersagen.It is known that many natural substances have biological effectiveness are optically active due to the presence of one or more asymmetric carbon atoms, i. rotate the plane of polarized light to the right (+) or left (-). Very often these connections have a higher *) than corresponding synthetically obtained, optically inactive compounds. The same applies to some synthetically produced active ingredients such as pharmaceuticals or pesticides with asymmetric carbon atoms, the usually in the synthesis as optically inactive racemates, i.e. mixtures of equal proportions of right-handed and left-handed Enantiomers. Here, too, it is not infrequently found in the separation of isomers that the effectiveness one of the two enantiomers is higher than that of the racemate. Whether the left (-) - or the right (+) - rotating form die is active in each case and whether there is any connection between effect and optical activity, however, can be do not predict.
Aus der Klasse der p-substituierten cC-Phenoxy-propionsäure-Derivate wurden in letzter Zeit Verbindungen bekannt, die wegen ihrer spezifisch grasherbiziden Wirkung von Interesse sind (z.B. DT-OS 22 23 894, DT-OS 24 33 067, DT-OS 25 31 64 3, DT-OS 26 17 804, DT-OS 26 23 558, DT-OS 25 46 251, DT-CS 24 17 487 und DT-OS 26 01 548J. Diese besitzen in Nachbarstellung zur Carbonylfunktion ein asymmetrisches C-Atan und werden daher bei der Synthese als Racemate erhalten.From the class of the p-substituted cC-phenoxy-propionic acid derivatives compounds have recently become known which are of interest because of their specific herbicidal effects are (e.g. DT-OS 22 23 894, DT-OS 24 33 067, DT-OS 25 31 64 3, DT-OS 26 17 804, DT-OS 26 23 558, DT-OS 25 46 251, DT-CS 24 17 487 and DT-OS 26 01 548J. These have in neighboring positions an asymmetric carbon atane to the carbonyl function and are therefore used in the Synthesis obtained as racemates.
Es wurde nun gefunden, daß die rechtsdrehenden Enantiomeren dieser Verbindungen sich durch eine erheblich höhere herbizide Wirksamkeit im Vergleich zu den Racematen auszeichnen. Die ( + )-Enantiomeren der CC-Phenoxy-propionsäurederivate leiten sich formal vom D-Glycerinaldehyd ab und werden daher mit D-(+) bezeichnet.It has now been found that the dextrorotatory enantiomers of these compounds are considerably higher herbicidal Effectiveness compared to the racemates. The (+) -enantiomers of the CC-phenoxy-propionic acid derivatives lead form formally from D-glyceraldehyde and are therefore with D - (+) denotes.
Gegenstand der Erfindung sind somit D- ( + )-OC-Phenoxy-propionsäurederivate
der Formel I
*) biologische WirksamkeitThe invention thus relates to D- (+) -OC-phenoxypropionic acid derivatives of the formula I.
*) biological effectiveness
909827/0199909827/0199
27530022753002
HiHi
CH-CH-
(I)(I)
in der
R eine Gruppe der Formelin the
R is a group of the formula
2 (V) 2 (V)
(VI)(VI)
Wasserstoff, Halogen oder CF3 Hydrogen, halogen or CF 3
Wasserstoff, (C1-C4)-Alkyl, Halogen oder NO3, mit der Maßgabe, daß / falls R einen Rest der Formel II, III oder VI bedeutet, R. Hydrogen, (C 1 -C 4 ) -alkyl, halogen or NO 3 , with the proviso that / if R is a radical of the formula II, III or VI, R.
nicht Wasserstoff ist,is not hydrogen,
Z eine Gruppe der FormelZ is a group of the formula
O
-C-O-R,,O
-COR ,,
O
-C-S-RO
-CSR
4'4 '
-C-N-C-N
O R7 OR 7
ti ι 'ti ι '
.-C-N-N.-C-N-N
oder -C-NH0,or -C-NH 0 ,
H, (C1-C12J-AlKyI, das gegebenenfalls durch 1 - 6 Halogenatome und/oder durch OH, (C1-Cg)-AIkOXy, (C1-C.)-Alkylthio, (C1-C6)-Alkoxy-(C2-Cg)-alkoxy, Halogen-(C1-C2)-alkoxy, Methoxy-äthoxy-äthoxy, (C1-C4)-Alkylair.ino, Di-(C1-C4)-alkylamino, Phenyl, Oxiranyl und Phenoxy substituiert ist, v/obei letzteres ebenfalls ein- bis zweifach durch Halogen und/oder (C1-C4)-Alkyl substituiert sein kann; (C5-Cg)-Cycloalkyl oder Halogen-(C5-Cg)-cycloalkyl, (C^-Cg)-Alkenyl, Halogen-(C3-Cg)-alkenyl oder (C5-Cg)-Cycloalkenyl, H, (C 1 -C 12 J-AlKyI, optionally substituted by 1 - 6 halogen atoms and / or by OH, (C 1 -Cg) -AIkOXy, (C 1 -C.) -Alkylthio, (C 1 -C 6 ) -Alkoxy- (C 2 -Cg) -alkoxy, halogen- (C 1 -C 2 ) -alkoxy, methoxy-ethoxy-ethoxy, (C 1 -C 4 ) -alkylair.ino, di- (C 1 -C 4 ) -alkylamino, phenyl, oxiranyl and phenoxy is substituted, v / whether the latter can also be substituted one or two times by halogen and / or (C 1 -C 4 ) -alkyl; (C 5 -Cg) -cycloalkyl or halogen - (C 5 -Cg) -cycloalkyl, (C ^ -Cg) -alkenyl, halogen- (C 3 -Cg) -alkenyl or (C 5 -Cg) -cycloalkenyl,
(C3-C4)-Alkinyl, das gegebenenfalls ein- oder zweifach durch (C1-Cg)-AIkYl, Phenyl, Halogen bzw. (C-.-C3)-Alkoxy substituiert ist,(C 3 -C 4 ) -alkynyl, which is optionally substituted once or twice by (C 1 -Cg) -alkYl, phenyl, halogen or (C -C 3 ) -alkoxy,
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Phenyl, das gegebenenfalls ein- bis dreifach durch (C1-C4)-Alkyl, (C1-C.)-Alkoxy, Halogen, NO» oder CF, substituiert ist, Furfuryl, Tetrahydrofurfuryi oder ein Kationäquivalent einer organischen oder anorganischen Base,Phenyl, which is optionally substituted one to three times by (C 1 -C 4 ) -alkyl, (C 1 -C.) -Alkoxy, halogen, NO »or CF, furfuryl, tetrahydrofurfuryi or a cation equivalent of an organic or inorganic base ,
R4 (C^-Cg Χ-Alkyl, das gegebenenfalls durch (C1-C-J)-AIkOXy t Halogen oder Phenyl substituiert ist, wobei letzteres ebenfalls ein- bis dreifach durch CC1-C4)-Alkyl und Halogen substituiert sein kann;R 4 (C ^ -Cg Χ-alkyl, which is optionally substituted by (C 1 -C - J) -AIkOXy t halogen or phenyl, the latter also being substituted one to three times by CC 1 -C 4 ) -alkyl and halogen can be;
(C3-Cg)-Alkenyl oder Phenyl, das gegebenenfalls ein- bis dreifach durch (C1-C4)-Alkyl und/oder Halogen substituiert ist,(C 3 -Cg) -alkenyl or phenyl, which is optionally substituted one to three times by (C 1 -C 4 ) -alkyl and / or halogen,
Rr und Rg gleich oder verschieden sind und H, (C--C6)-Alkyl, Hydroxy-(C1-C&)-alkyl, (C5-Cg)-Cycloalkyl oder Phenyl, das gegebenenfalls ein- bis dreifach durch (C1-C4)-Alkyl, (Cj-C4)-Alkoxy, Halogen oder CF3 substituiert ist (mit der Maßgabe, daß R5 und Rg nicht gemeinsam Phenyl sind), bedeuten oder gemeinsam eine Methylenkette mit 2, 4 oder Gliedern bilden, in der eine CH~-Gruppe gegebenenfalls durch O, NH oder N(CH3) ersetzt sein kann,Rr and Rg are identical or different and are H, (C - C6) alkyl, hydroxy (C 1 -C) alkyl, (C 5 -CG) -cycloalkyl or phenyl which is optionally mono- to trisubstituted by (C 1 -C 4 ) -alkyl, (Cj-C 4 ) -alkoxy, halogen or CF 3 is substituted (with the proviso that R 5 and Rg are not phenyl together), or together are a methylene chain with 2, 4 or form members in which a CH - group can optionally be replaced by O, NH or N (CH 3 ),
R7 H oder CH3,R 7 H or CH 3 ,
R8 H, CH3 oder C3H5,R 8 H, CH 3 or C 3 H 5 ,
Rq H, CH3, C3Hc- oder PhenylRq H, CH 3 , C 3 Hc- or phenyl
bedeuten mit der Einschränkung, daß wenn R1 Trifluormethyl, R2 Wasserstoff und R eine Gruppe der Formel II sind, R3 nicht Wasserstoff ist.mean with the restriction that when R 1 is trifluoromethyl, R 2 is hydrogen and R is a group of the formula II, R 3 is not hydrogen.
In der vorliegenden Beschreibung bedeutet Halogen stets Chlor oder Brom.In the present description, halogen always means chlorine or bromine.
Man erhält die genannten Verbindungen, indem manThe compounds mentioned are obtained by
a) entsprechend substituierte Phenole oder Phenolate der allgemeinen Formela) appropriately substituted phenols or phenolates of the general formula
■■O--■■ O--
(VII)(VII)
in der X ein Alkaliatom oder Wasserstoff bedeutet, mit sub-in which X is an alkali atom or hydrogen, with sub-
909827/0199909827/0199
stituierten L-Propionsäureestern der allgemeinen Formelsubstituted L-propionic acid esters of the general formula
CH3 CH 3
in der Y Chlor, Brom oder eine Sulfonyloxygruppe bedeutet
oder
b) falls R einen Rest der Formel m, iv oder V bedeutet,in which Y is chlorine, bromine or a sulfonyloxy group or
b) if R is a radical of the formula m, iv or V,
auch Verbindungen der Formel Zalso compounds of the formula Z
.0-.0-
(IX)(IX)
CH3 CH 3
mit einem entsprechend substituierten 2-Halogen-pyridin, -benzthiazol oder -benzoxazol umsetzt,with an appropriately substituted 2-halopyridine, -benzthiazole or -benzoxazole converts,
und gewünschtenfalls die erhaltenen Verbindungen der Formel I in andere Verbindungen der Formel I überführt.and, if desired, the compounds of the formula I obtained converted into other compounds of formula I.
Bei dem erfindungsgemäßen Verfahren nach a) findet eine Waldensche Umkehrung statt, wobei die L-Konfiguration des Propionsäurederivates in die D-Konfiguration des Endproduktes übergeht.In the method according to the invention according to a) there is a Waldenscheid Reversal takes place, with the L-configuration of the propionic acid derivative merges into the D configuration of the end product.
a) Zur Durchführung des Verfahrens a) bedient man sich allgemein bekannter Verfahrensbedingungen. Bei Verwendung einesa) To carry out the process a) one uses generally known process conditions. When using a
^bevorzugt^ preferred
Phenols als Ausgangsmaterial (X = H) arbeitet manjin Gegenwart eines Alkalicarbonate als Säurefänger und in einem polaren Lösungsmittel, vorzugsweise Aceton, Methyläthylketon, Acetonitril, Dimethylformamid oder Dimethylsulfoxyd bei Temperaturen zwischen 50 und 1500C. Verwendet man als Ausgangsverbindung der Formel VII ein Phenolat (X = Alkaliatom, vorzugsweise Na oder K), so empfiehlt sich die Anwendung von hochsiedenden Lösungsmitteln wie Toluol, Xylol, DIlF oder DMSO und von Tempe-Phenol as the starting material (X = H) is used in the presence of an alkali metal carbonate as an acid scavenger and in a polar solvent, preferably acetone, methyl ethyl ketone, acetonitrile, dimethylformamide or dimethyl sulfoxide at temperatures between 50 and 150 ° C. If the starting compound of formula VII is a phenolate ( X = alkali atom, preferably Na or K), then the use of high-boiling solvents such as toluene, xylene, DIlF or DMSO and of tempe-
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raturen von 100 - 1500C. Unter der Sulfonyloxygruppe in Y ist
die Gruppe R10-SO-O- zu verstehen, in der R10 einen aliphatischen
oder aromatischen Rest bedeutet, vorzugsweise der
Mesylatrest (CH3SO2Q -), der Rest CF-SO-O-, der Benzolsulfonatrest,
der Tosylatrest (P-CH3-C6H4-SO2O-) oder ein durch N0_
oder OCH3 substituierter Benzolsulfonatrest.temperatures from 100 to 150 0 C. Under the sulfonyloxy group in Y is understood to 10 -SO-O-, the group R 10 is an aliphatic or aromatic radical in which R, preferably the
Mesylate residue (CH 3 SO 2 Q -), the residue CF-SO-O-, the benzenesulfonate residue, the tosylate residue (P-CH 3 -C 6 H 4 -SO 2 O-) or a by N0_
or OCH 3 substituted benzenesulfonate radical.
b) Die Umsetzung gemäß b) verläuft unter den gleichen Bedingungen wie a). Die Ausgangsverbindungen der Formel IX erhält man aus Hydrochinon-monobenzyläther bzw. dessen Alkalisalzen der Formelb) The reaction according to b) proceeds under the same conditions as a). The starting compounds of the formula IX are obtained from hydroquinone monobenzyl ether or its alkali metal salts of the formula
-O-X (X)-O-X (X)
durch Umsetzung mit Verbindungen der FormelVIII und hydrogenolytische Abspaltung der Benzylgruppe. Als Katalysatoren eignen sich besonders Edelmetallkatalysatoxen wie Palladium/Tierkohle.by reaction with compounds of the formula VIII and hydrogenolytic Splitting off of the benzyl group. Noble metal catalytic converters such as palladium / animal charcoal are particularly suitable as catalysts.
Die nach a) oder b) erhaltenen Verbindungen der Formel I kann man gewünschtenfalls durch allgemein bekannte Operationen in
andere Verbindungen der Formel I überführen. So erhält man
aus Estern durch alkalische Verseifung Salze (R3 = Kat), die
wiederum in die freien Säuren ^R3 = H)The compounds of the formula I obtained according to a) or b) can, if desired, be converted into other compounds of the formula I by generally known operations. So you get
from esters by alkaline saponification salts (R 3 = Kat), which in turn are converted into the free acids ^ R 3 = H)
überführt werden können. Letztere liefern auf dem Umv?eg über die Säurehalogenide die entsprechenden Amide, Hydrazide oder Thioester. Durch Veresterung der freien Säuren oder der Säurechloride oder durch direkte Umesterung entstehen andere Ester der Formel I.can be transferred. The latter supply the corresponding amides, hydrazides or in the vicinity via the acid halides Thioester. Other esters are formed through esterification of the free acids or acid chlorides or through direct transesterification of formula I.
Bei Verwendung von optisch reinem Ausgangsmaterial liefern die erfindungsgemäßen Verfahren Endprodukte mit einer optischen Reinheit
von mindestens 60 % entsprechend einem Anteil von 80 %
der (+)-Form. Wenn gewünscht, kann die optische Reinheit der Verbindungen nach üblichen Verfahren, z.B. Umkristallisation
v/eiter erhöht werden. Falls diese Verbindungen, insbesondere die Ester, flüssig sind, ist es ein bevorzugtes Reinigungsverfahren,
die zunächst erhaltenen Ester zur entsprechenden Phenoxypropionsäure zu verseifen, diese in an sich bekannter Weise
durch Umkristallisation von etwa vorhandenen geringen Mengen der L-Form zu reinigen und dann aus der weitgehend reinen Säure
nach einem der vorstehend angegebenen Verfahren die gewünschten Verbindungen der Formel I herzustellen.When using optically pure starting material, the processes according to the invention provide end products with an optical purity of at least 60%, corresponding to a proportion of 80%
the (+) form. If desired, the optical purity of the compounds can be increased by customary processes, for example recrystallization. If these compounds, in particular the esters, are liquid, a preferred purification process is to saponify the esters initially obtained to give the corresponding phenoxypropionic acid, this in a manner known per se
to purify any small amounts of the L-form present by recrystallization and then to prepare the desired compounds of the formula I from the largely pure acid by one of the processes given above.
9 09827/01999 09827/0199
- IO -- OK -
Bevorzugte Verbindungen der Formel I sind solche, in denen das Paar R1ZR3 H/c1' H/Br, H/CF3, 01/CF3, Cl/Cl, Cl/Br bzw. (wenn R einen Rest der Formel IV oder V darstellt) auch H/H bedeutet. Bedeutet R einen Rest der Formel II oder VI, so befinden sich die Reste R.j und R3 bevorzugt in 4- oder in 2,4-Stellung, während bei R = Rest der Formel III die Positionen 5 und 3,5 bzw. bei R = Rest der Formel IV oder V die Positionen 5 und 6 besonders bevorzugt sind.Preferred compounds of the formula I are those in which the pair R 1 ZR 3 H / c1 'H / Br, H / CF 3 , 01 / CF 3 , Cl / Cl, Cl / Br or (when R is a radical of the formula IV or V) also means H / H. If R is a radical of the formula II or VI, the radicals Rj and R 3 are preferably in the 4- or 2,4-position, while when R = radical of the formula III, the positions 5 and 3.5 or in R = Radical of the formula IV or V the positions 5 and 6 are particularly preferred.
Außer den in den Beispielen aufgeführten Verbindungen sind folgende Verbindungen besonders wirksam:In addition to the compounds listed in the examples, the following compounds are particularly effective:
D-(+)-2-/4-(4-Chlorphenoxy)-phenoxy_7-propionsäure, D-(+)-2-/4-(4-Chlorphenoxy)-phenoxy_7-propionsäure-methylester, -n-propylester, -isoamylester,D - (+) - 2- / 4- (4-chlorophenoxy) -phenoxy_7-propionic acid, D - (+) - 2- / 4- (4-chlorophenoxy) -phenoxy_7-propionic acid methyl ester, -n-propyl ester, -isoamyl ester,
D-(+)-2-/4-(2,4-Dichlorphenoxy)-phenoxy_7-propionsäure, Natrium-D-i+)-2-/4-(2,4-Dichlorphenoxy)phenoxy_7-propionat, Dimethylainmonium-D-( + )-2-/4-(2,4-Dichlorphenoxy)-phenoxy_7~ propionat,D - (+) - 2- / 4- (2,4-dichlorophenoxy) -phenoxy_7-propionic acid, Sodium D-i +) - 2- / 4- (2,4-dichlorophenoxy) phenoxy_7-propionate, Dimethylainmonium-D- (+) -2- / 4- (2,4-dichlorophenoxy) -phenoxy_7 ~ propionate,
D(+)-2-/Ϊ-(2,4-Dichlorphenoxy)-phenoxy_7-propionsäure-isopropylester, -isobutylester, -n-amylester,D (+) - 2- / Ϊ- (2,4-dichlorophenoxy) -phenoxy_7-propionic acid isopropyl ester, -isobutyl ester, -n-amyl ester,
D-{+)-2-/4-(4-Brom-2-chlorphenoxy)-phenoxy_7-propionsäure-npropylester, D - {+) - 2- / 4- (4-Bromo-2-chlorophenoxy) -phenoxy_7-propionic acid n-propyl ester,
Kalium-D-(+)-2-/4-(4-Brom-2-chlorphenoxy)-phenoxy 7-propionat, Diathylammonium-D-( + )-2-/4-(4-Brom-2-chlorphenoxy)-phenoxy_7~ propionat,Potassium D - (+) - 2- / 4- (4-Bromo-2-chlorophenoxy) -phenoxy 7-propionate, Dietammonium-D- (+) -2- / 4- (4-Bromo-2-chlorophenoxy) -phenoxy_7 ~ propionate,
D- ( + ) -2-/4- (4-Brom-2-chlorphenoxy) -phenoxy_7-propionsäure-secamylester, D- (+) -2- / 4- (4-bromo-2-chlorophenoxy) -phenoxy_7-propionic acid secamyl ester,
Ammonium-D-(+)-2-/?-(4-Trifluormethylphenoxy)-phenoxy_7~propionat, Methylammonium-D- ( + ) -2-/4- (4-Trif luormethylphenoxy) pheiioxy_7~ propionat,Ammonium D - (+) - 2 - /? - (4-Trifluoromethylphenoxy) -phenoxy_7 ~ propionate, Methylammonium-D- (+) -2- / 4- (4-trifluoromethylphenoxy) pheiioxy_7 ~ propionate,
D- ( + ) -2-/Ϊ- (4-Trif luormethylphenoxy )-phenoxy_?propionsäuren-propylester, -isobutylester,D- (+) -2- / Ϊ- (4-trifluoromethylphenoxy) -phenoxy_? Propionic acid propyl ester, isobutyl ester,
D( + ) -2-/4-(2Chlor-4-Trif luormethyl-phenoxy) -phenoxy 7propionsäure, -methylester, -aethylester, n- und i-propylester, n- und i-buty!ester, -Na- und K-SaIz, D (+) -2- / 4- (2-chloro-4-trifluoromethyl-phenoxy) -phenoxy-7propionic acid, -methylester, -aethylester, n- and i-propylester, n- and i-butylester, -Na- and K-SaI z,
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D-(+)-2-/3-(4-Chlorbenzyl)-phenoxy_7-propionsSuref D-(♦)-2-/~4-(4-Chlorbenzyll-phenoxy_7-propionsäure-methylesterr -äthylester, -isobuty!ester,D - (+) - 2- / 3- (4-chlorobenzyl) -phenoxy_7-propionic acid f D- (♦) -2- / ~ 4- (4-chlorobenzyl-phenoxy_7-propionic acid methyl ester r -ethyl ester, -isobuty! ester,
D- {+) -2-/4- (2,4-Dichlorbenzyll -phenoxy^-propionsäure-n-propylester, -isoamy!ester, -äthylester,D- {+) -2- / 4- (2,4-dichlorobenzyl-phenoxy ^ -propionic acid n-propyl ester, -isoamy! ester, -ethyl ester,
D-(+)-2-/?-(2,4-Dichlorbenzylf-phenoxy_7-propionsäure, Natrium-D-{+)-2-£4-(2,4-Dichlorbenzyiy-phenoxy_7-propionat, D-(+)-2-/Ϊ-(3,5-Dichlor-2-pyridyloxy)-phenoxy_7-propionsäure, D-(+)-2-/4-(3,5-Dichlor-2-pyridyloxy>-phenoxy_7-propionsäuremethylester, -äthylester, -propy!ester, -isopropylester, -isobutylester, -Natriumsalz,D - (+) - 2 - /? - (2,4-dichlorobenzylf-phenoxy_7-propionic acid, Sodium D - {+) - 2- £ 4- (2,4-Dichlorbenzyiy-phenoxy_7-propionat, D - (+) - 2- / Ϊ- (3,5-dichloro-2-pyridyloxy) -phenoxy_7-propionic acid, D - (+) - 2- / 4- (3,5-dichloro-2-pyridyloxy> -phenoxy_7-propionic acid methyl ester, ethyl ester, propy ester, isopropyl ester, isobutyl ester, sodium salt,
D-(+)-2-/4-(5-Chlor-2-benzoxazolyloxy)-phenoxy_7-propionsäuremethylester, -äthylester, -propylester, -isopropylester, -isobutylester,D - (+) - 2- / 4- (5-chloro-2-benzoxazolyloxy) -phenoxy_7-propionic acid methyl ester, ethyl ester, propyl ester, isopropyl ester, isobutyl ester,
D-(+)-2-£5-(6-Chlor-2-benzoxazolyloxy)-phenoxy_7-propionsäuremethylester, -äthylester, -propylester, -isopropylester, -isobutylester, D - (+) - 2- £ 5- (6-chloro-2-benzoxazolyloxy) -phenoxy_7-propionic acid methyl ester, ethyl ester, propyl ester, isopropyl ester, isobutyl ester,
D-(+)-2-^4-(6-Chlor-2-benzthiazolyloxy)-phenoxy_7~propionsäuremethylester, -äthylester, -propylester, -isopropylester, -isobutylester,D - (+) - 2- ^ 4- (6-chloro-2-benzthiazolyloxy) -phenoxy_7 ~ propionic acid methyl ester, ethyl ester, propyl ester, isopropyl ester, isobutyl ester,
D-(+)-2-11-(2-Benzthiazolyloxy)-phenoxy_7-propionsaure-methylester, -äthylester,D - (+) -2-11- (2-Benzthiazolyloxy) -phenoxy_7-propionic acid methyl ester, ethyl ester,
D-(+)-2-/3-(2-Benzoxazolyloxy)-phenoxy_7-propionsäure-methylester, -äthylester,D - (+) - 2- / 3- (2-Benzoxazolyloxy) -phenoxy_7-propionic acid methyl ester, ethyl ester,
D-(+)-2-[A-(6-Brom-2-benzthiazolyloxy)-phenoxy_7-propionsäureäthylester, D - (+) -2- [A- (6-bromo-2-benzthiazolyloxy) -phenoxy_7-propionic acid ethyl ester,
D-(+)-2-/4-(6-Brom-2-benzoxazolyloxy)-phenoxy_7~propionsäureäthylester. D - (+) - 2- / 4- (6-bromo-2-benzoxazolyloxy) -phenoxy_7 ~ propionic acid ethyl ester.
Ferner seien folgende Verbindungen genannt:The following compounds may also be mentioned:
D-(+)-2-/4-(4-Chlorphenoxy)phenoxy_7-propionsäure-2-chloräthylester, -2,3-dichlor-n-propylester, -cyclohexylester, -propargyl-, -äthylthiolester, -dimethylamid,D - (+) - 2- / 4- (4-chlorophenoxy) phenoxy_7-propionic acid-2-chloroethyl ester, -2,3-dichloro-n-propylester, -cyclohexylester, -propargyl-, -äthylthiolester, -dimethylamid,
D- ( + ) -2-/4-<2,4-Dichlorphenoxy) -phenoxy_7-propionsäure-2-methylaminoäthylester, -allylester, -3,4-dichlorbenzylester, -diäthylamid, -*N-methylhydrazid, -thioamid,D- (+) -2- / 4- <2,4-dichlorophenoxy) -phenoxy_7-propionic acid-2-methylaminoethyl ester, allyl ester, -3,4-dichlorobenzyl ester, diethylamide, - * N-methylhydrazide, -thioamide,
D- ( + ) -2-/4*- (4-Brom-2-chlorphenoxy) -phenoxy_7-propionsäure-2-D- (+) -2- / 4 * - (4-Bromo-2-chlorophenoxy) -phenoxy_7-propionic acid-2-
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äthylthioäthylester, -N-ri-propylaminoäthylester, -2-chlorallylester, -4-chlorbenzylthiolester, -phenylhydrazid, D- ( + ) -2-/4- (4-Trif luormethyf^'-phenoxy_7-propionsäure-2- (4-chlorphenyl)-äthylester, -n-oc tylester, -methallylester, -(3-phenyl)-propargylester, -n-propylamid,ethylthioethyl ester, -N-ri-propylaminoethyl ester, -2-chlorallyl ester, -4-chlorobenzylthiol ester, -phenylhydrazide, D- (+) -2- / 4- (4-trifluoromethyf ^ '- phenoxy_7-propionic acid 2- (4-chlorophenyl) ethyl ester, -n-oc tylester, -methallylester, - (3-phenyl) -propargylester, -n-propylamide,
D-(+)-2-/4-(2,4-Dichlorbenzyl)-phenoxy_7-propionsäure-n-dodecylester, -benzylthiolester, -cyclohexylamid, -^N,2N-dimethylhydrazid, D - (+) - 2- / 4- (2,4-dichlorobenzyl) -phenoxy_7-propionic acid-n-dodecylester, -benzylthiolester, -cyclohexylamide, - ^ N, 2 N-dimethylhydrazide,
D- ( + ) -2-/~4- (4-Chlorbenzyl) -phenoxy_7-propionsäure-cyclopentylester, -äthoxyäthylamid.D- (+) -2- / ~ 4- (4-chlorobenzyl) -phenoxy_7-propionic acid cyclopentyl ester, ethoxyethylamide.
D- ( + ) -2-/3- (2-Chlor-4-t.rif luormethylphenoxy) -phenoxy_7-propionsäure-äthylester, -2-methoxyäthylester, -n-hexylester, -cyclohexylester, -amid, -anilid, -p-chloranilid, D-(+)-2-^4-(5-Chlor-2-pyridyloxy)-phenoxy_7~propionsäure, D- ( + ) -2-/3- (5--Chlor-2-pyridyloxy) -phenoxy_7-propionsäure-methylester, -isoamylester, -methoxyäthylester, -3-methoxybuty!ester, -2-chlorpropylester, -allylester, -propargylester, D-(+)-2-/3-(5-Brom-2-pyridyloxy)-phenoxy_7~propionsäure, D-(+)-2-/3-(5-Brom-2-pyridyloxy)-phenoxy_7-propionsäure-methylester, -äthylester, -amid, -dimethylamid, -hydrazid, -anilid, D-(+)-2-^4-(3,5-Dichlor-2-pyridyloxy)-phenoxy_7~propionsäureisobutylester, -2-chloräthylester, -1-methylpropargylester, -cyclohexylester, -cyclohexenylester, -2-chlorcyclohexylester, -butoxyäthylester, -methoxyäthoxyäthylester, -6-chlorhexylester, -amid, -dimethylamid, -diäthylamid, -anilid, -Kaliumsalz, -Ammoniumsalz, -dimethylammoniumsalz,D- (+) -2- / 3- (2-chloro-4-t.rif luoromethylphenoxy) -phenoxy_7-propionic acid ethyl ester, -2-methoxyethyl ester, -n-hexyl ester, -cyclohexyl ester, -amid, -anilid, -p-chloranilide, D - (+) - 2- ^ 4- (5-chloro-2-pyridyloxy) -phenoxy_7 ~ propionic acid, D- (+) -2- / 3- (5 - chloro-2-pyridyloxy) -phenoxy_7-propionic acid methyl ester, -isoamyl ester, methoxyethyl ester, -3-methoxybutyl ester, -2-chloropropyl ester, -allyl ester, -propargyl ester, D - (+) - 2- / 3- (5-bromo-2-pyridyloxy) -phenoxy_7 ~ propionic acid, D - (+) - 2- / 3- (5-bromo-2-pyridyloxy) -phenoxy_7-propionic acid methyl ester, -äthylester, -amid, -dimethylamid, -hydrazid, -anilid, D - (+) - 2- ^ 4- (3,5-dichloro-2-pyridyloxy) -phenoxy_7 ~ propionic acid isobutyl ester, -2-chloroethyl ester, -1-methylpropargyl ester, -cyclohexylester, -cyclohexenylester, -2-chlorocyclohexylester, -butoxyäthylester, -methoxyäthoxyäthylester, -6-chlorhexylester, -amid, -dimethylamide, -diethylamide, -anilide, -potassium salt, -ammonium salt, -dimethylammonium salt,
D- ('+) -2-/4- (3-Chlor-5-brom-2-pyridyloxy) -phenoxy_7-propionsäure, D- ( + )-2-/4-(3-Chlor-5-brom-2-pyridyloxy)-phenoxy_7-propionsäuremethylester, -äthylester,D- ('+) -2- / 4- (3-chloro-5-bromo-2-pyridyloxy) -phenoxy_7-propionic acid, D- (+) -2- / 4- (3-chloro-5-bromo-2-pyridyloxy) -phenoxy_7-propionic acid methyl ester, ethyl ester,
D-(+)-2-/4-(3-Brom-5-chlor-2-pyridyloxy)-phenoxy_7~propionsäureisopropylester, D - (+) - 2- / 4- (3-bromo-5-chloro-2-pyridyloxy) -phenoxy_7 ~ propionic acid isopropyl ester,
D- ( + )-2-/3-(5-Chlor-3-methyl-2-pyridyloxy)-phenoxy_7~propionsäure, D- (+) -2- / 3- (5-chloro-3-methyl-2-pyridyloxy) -phenoxy_7 ~ propionic acid,
D- ( + ) -2-/4- (5-Chlor-3-methyl-2-pyridyloxy) -phenoxy_7-pj-*opionsäure-methylester, -äthylester,D- (+) -2- / 4- (5-chloro-3-methyl-2-pyridyloxy) -phenoxy_7-pj- * opionic acid methyl ester, ethyl ester,
D-(+)-2-/3-(2-Benzthiazolyloxy)-phenoxy_7-p*°pionsäure-isobutylester, -3-chlorpropylester, -allylester, -1-phenylpropargyl- ester, -amid,D - (+) - 2- / 3- (2-Benzthiazolyloxy) -phenoxy_7-p * ° pionic acid isobutyl ester, -3-chloropropyl ester, allyl ester, -1-phenylpropargyl ester, amide,
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D-(+)-2-/4-(5-Chlor-2-benzthiazolyloxy)-phenoxy_7-propionsäuremethylester, -äthylester, -isobutylester, D-(+)-2-^4-(6-Chlor-2-benzthiazolyloxy)-phenoxy_7-propionsäureisoamylester, -isooctylester, -2-chloräthylester, -3-chlorpropylester, -1,3-dichlorisopropylester, -6-chlorhexylester, -2-raethoxyäthylester, -2-butoxyäthylester, -3-methoxybutylester, -allylester, -cyclohexylester, -1,1-dimethylpropargylester, -cyclohexenylester,D - (+) - 2- / 4- (5-chloro-2-benzthiazolyloxy) -phenoxy_7-propionic acid methyl ester, ethyl ester, isobutyl ester, D - (+) - 2- ^ 4- (6-chloro-2-benzthiazolyloxy) -phenoxy_7-propionic acid isoamyl ester, -isooctyl ester, -2-chloroethyl ester, -3-chloropropyl ester, -1,3-dichloroisopropyl ester, -6-chlorhexyl ester, -2-methoxyethyl ester, -2-butoxyethyl ester, -3-methoxybutyl ester, allyl ester, cyclohexyl ester, -1,1-dimethylpropargyl ester, -cyclohexenyl ester,
D- ( + ) -7.-(Ji- (6-Trifluormethyl-2-benzthiazolyloxy) -phenoxy ~J-propionsäure-methylester, -äthylester, -propylester, -isopropylester, -isobutylester,D- (+) -7 .- (Ji- (6-trifluoromethyl-2-benzthiazolyloxy) -phenoxy ~ J- propionic acid methyl ester, ethyl ester, propyl ester, isopropyl ester, isobutyl ester,
D-(+)-2-/4-(5-Trifluormethyl-2-benzthiazolyloxy)-phenoxy_7-propionsäure-methylester, -äthylester, D-(+)-2-^4-(6-Brom-2-benzthiazolyloxy)-phenoxy_7-propionsäuremethylester, -propylester, -isobutylester, D-(+)-2-/4-(5-Brom-2-benzthiazolyloxy)-phenoxy_7-propionsäureäthy1ester, D - (+) - 2- / 4- (5-trifluoromethyl-2-benzthiazolyloxy) -phenoxy_7-propionic acid methyl ester, ethyl ester, D - (+) - 2- ^ 4- (6-bromo-2-benzthiazolyloxy) -phenoxy_7-propionic acid methyl ester, -propylester, -isobutylester, D - (+) - 2- / 4- (5-bromo-2-benzthiazolyloxy) -phenoxy_7-propionic acid ethyl ester,
D- ( + ) -2-IJi- (5-Brom-2-benzoxazolyloxy) -phenoxy) -propionsäuremethylester, -äthylester, -isopropylester, -isobutylester, D-(+)-2-/4-(6-Brom-2-benzoxazolyloxy^-phenoxy_7-propionsäuremethylester, -propylester, -isobutylester, D- ( + ) -2-^4- (6-Trif luormethyl-2-benzoxazolyloxy) -phenoxy J-propionsäure-methylester, -äthylester, -propylester, D-(+)-2-^4-(5-Chlor-2-benzoxazolyloxy)-phenoxy_7-propionsäureisoamylester, -2-chloräthylester, -3-chlorpropylester, -2-methoxyäthylester, -3-methoxybutylester, -methoxyäthoxyäthylester, -cyclohexylester, -allylester, propargylester, D-(+)-2-/4-(6-Chlor-2-benzoxazolyloxy)-phenoxy_7~propionsäureisobutylester, -1,3-dichlorisopropylester, -6-chlorhexylester, -1-methoxyäthylester, -cyclohexylester, -2-chlorcyclohexylester, -1-äthylpropargylester.D- (+) -2-IJi- (5-bromo-2-benzoxazolyloxy) phenoxy) propionic acid methyl ester, ethyl ester, isopropyl ester, isobutyl ester, D - (+) - 2- / 4- (6-bromo) 2-benzoxazolyloxy ^ -phenoxy_7-propionate, propyl, isobutyl, D- (+) -2- ^ 4- (6-trifluoromethyl-2-benzoxazolyloxy) phenoxy J- propionate, ethyl ester, propyl ester, D - (+) - 2- ^ 4- (5-chloro-2-benzoxazolyloxy) -phenoxy_7-propionic acid isoamyl ester, -2-chloroethyl ester, -3-chloropropyl ester, -2-methoxyethyl ester, -3-methoxybutyl ester, -methoxyethoxyethyl ester, -cyclohexyl ester , -allyl ester, propargyl ester, D - (+) - 2- / 4- (6-chloro-2-benzoxazolyloxy) -phenoxy_7 ~ propionic acid isobutyl ester, -1,3-dichloroisopropyl ester, -6-chlorhexyl ester, -1-methoxyethyl ester, -cyclohexyl ester , -2-chlorocyclohexyl ester, -1-ethyl propargyl ester.
Wie eingangs erwähnt, zeichnen sich die erfindungsgemäßen D-(+)-Enantiomeren gegenüber den vorbeschriebenen Racematen durch eine erheblich gesteigerte herbizide Wirkung aus. überraschenderweise zeigte sich, daß die L-(-)-Enantiomere^ im Nachauflauf praktisch unwirksam sind. Die Wirksamkeit derAs mentioned at the outset, those according to the invention are distinguished D - (+) - enantiomers compared to the above-described racemates by a considerably increased herbicidal effect. Surprisingly, it was found that the L - (-) - enantiomers ^ im Post-emergence are practically ineffective. The effectiveness of the
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Racemate beruht somit praktisch allein auf ihrem Gehalt an D-{+)-Enantiomeren.Racemate is thus practically based solely on its content D - {+) - enantiomers.
Gegenstand der Erfindung sind somit auch herbizide Mittel, die gekennzeichnet sind durch einen Gehalt an einem Wirkstoff der Formel I in Kombination mit üblichen Hilfs- und Trägerstoffen. Die Formulierung für die praktische Anwendung erfolgt nach denselben Methoden und mit den gleichen Zusatzstoffen wie sie für die Racemate bereits bekannt sind. Bevorzugte Formulierungen sind Flüssigformulierungen oder ULV-Formulierungen. Die Formulierungen enthalten die Wirkstoffe vorzugsweise zu 2 - 95 % je nach Zubereitungsart. Wegen ihrer besseren Wirksamkeit kann mit den erfindungsgemäßen optisch aktiven Wirkstoffen die erforderliche Aufwandmenge pro Flächeneinheit gegenüber den Racematen um bis zu 60 % reduziert v/erden; sie liegt im allgemeinen zwischen 0.01 - 5 kg/ha, vorzugsweise bei 0.05 bis 3 kg/ha.The invention thus also relates to herbicidal compositions which are characterized by an active ingredient content of the formula I in combination with customary auxiliaries and carriers. The formulation for the practical application is carried out according to the same methods and with the same additives as they are already known for the racemates. Preferred formulations are liquid formulations or ULV formulations. The formulations preferably contain 2 to 95% of the active ingredients, depending on the type of preparation. Because of their better effectiveness can use the optically active ingredients according to the invention to achieve the required application rate per unit area compared to the racemates reduced by up to 60%; it is generally between 0.01-5 kg / ha, preferably at 0.05 to 3 kg / ha.
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Beispiel 1:Example 1:
D-(+D - (+ )-2-/4-) -2- / 4- (4-Chlorphenoxy)-phenoxy7-propionsäure-äthylesterEthyl (4-chlorophenoxy) phenoxy7-propionate
CO8C8H6 CO 8 C 8 H 6
220,5 g (1,0 Mol) 4-(4~Chlorphenoxy)-phenol werden mit 299,2 g (1,1 Mol) L-(-)-Milchsäureäthylester-tosyIat und 158,7 g (1,15 Mol) gepulvertem, wasserfreiem Kaliumcarbonat in 1000 ml Methylethylketon 56 Stunden zum Sieden unter Rückfluß erhitzt. 220.5 g (1.0 mol) 4- (4 ~ chlorophenoxy) -phenol are with 299.2 g (1.1 mol) of L - (-) - ethyl lactate tosyIate and 158.7 g (1.15 mol) of powdered, anhydrous potassium carbonate in 1000 ml of methyl ethyl ketone were heated to boiling under reflux for 56 hours.
Nach Erkalten wird vom Salzrückstand abfiltriert, das Lösungsmittel abgedampft und der verbleibende Rückstand im Hochvakuuc destilliert.After cooling, the salt residue is filtered off, the solvent evaporated and the remaining residue is distilled in a high vacuum.
Man erhält 310 g (97 # d. Th.) D-(+)-2-^T-(4-Chlorphenoxy)-phenoxy7-propionsäure-äthylester, Sdp. 159°C/OfO4 mm, aD2° = 6'5° ^1 m» Chloroform).This gives 310 g of D (97 # of theory..) - (+) - 2- ^ T- (4-chlorophenoxy) propionic acid ethyl ester -phenoxy7-, bp 159 ° C / f O O4 mm, a D 2 °. = 6 ' 5 ° ^ 1 m > chloroform).
9OOH9OOH
CH9 CH 9
32,1 g (0,10 Mol) D-(+)~2~/?-(4-Chlorphenoxy)-phenoxv7-propionsäure-äthylester werden in 150 ml Methanol gelöst und unter Rühren mit 125 ml 2n Natronlauge (0,25 Mol) versetzt. Man erhitzt 2 Stunden auf Siedetemperatur, destilliert anschließend den größten Teil des organischen Lösungsmittels 32.1 g (0.10 mol) of D - (+) ~ 2 ~ /? - (4-chlorophenoxy) -phenoxv7-propionic acid ethyl ester are dissolved in 150 ml of methanol and mixed with 125 ml of 2N sodium hydroxide solution (0.25 Mole) . The mixture is heated to boiling temperature for 2 hours, then most of the organic solvent is distilled
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ab und fällt nach Erkalten das Produkt durch Zugabe von Salzsäure. Nach Absaugen, Waschen mit Wasser und Trocknen erhält man 28,5 g (97 # d. Th.) D-(+)-2-/T-(4-Chlorphenoxy)-phenoxy7-propionsäure, Schap. 105° -1100C, aD 20 = 1,6° (0,4 nun, Chloroform). and after cooling the product falls by adding hydrochloric acid. After filtering off with suction, washing with water and drying, 28.5 g (97% of theory) of D - (+) - 2- / T- (4-chlorophenoxy) phenoxy7-propionic acid, Schap. 105 ° -110 0 C, a 20 D = 1.6 ° (0.4 now, chloroform).
D-(+)-2-/T-(4-Chlorphenoxy^phenoxy^-propionsaure-isobutylestcr D - (+) - 2- / T- (4-chlorophenoxy ^ ph enox y ^ -propionic acid isobutyl ester
CO2CH2CH(CH3 )2 CO 2 CH 2 CH (CH 3 ) 2
CH3 CH 3
Α«,.Durch Umesterung Α «,. By transesterification
160,3 g (0,5 Mol) D-( + )-2-/4"-(4-Chlorphenoxy)-phenoxy.7-propionsäure-äthylester werden in 500 ml Jsobuty!alkohol gelöst. Nach Zugabe von 2 ml konz. Schwefölsäure erhitzt man 8 Stunden zum Sieden, wobei über eine Kolonne das entstehende Aethanol abgenommen wird. Man destilliert anschließend das Lösungsmittel im Wacserstrahlvakuum weitgehend ab, nimmt den Rückstand in Methylenchlorid auf und wäscht mit V/asser. Nach Abdestillieren des Methylenchlorids destilliert man das Produkt im Hochvakuum .160.3 g (0.5 mol) of D- (+) -2- / 4 "- (4-chlorophenoxy) -phenoxy-7-propionic acid, ethyl ester are dissolved in 500 ml of jsobuty alcohol. To Addition of 2 ml of conc. Sulfur oleic acid is heated for 8 hours Boiling, the resulting ethanol being removed via a column. The solvent is then distilled in the water jet vacuum largely decreases, the residue takes in Methylene chloride and washes with water. After the methylene chloride has been distilled off, the product is distilled in a high vacuum .
Man erhält 159,0 g (91 # d. Th.) D-(+)-2-/?-(4-Chlorphenoxy)-phenoxyTpropionsäure-icobutylestsr, Sdp. 169° - 173°C/O,O5 mm, ο «ο s 7,4° (l mf Chloroform).159.0 g (91 # of theory) D - (+) - 2 - /? - (4-chlorophenoxy) -phenoxy-propionic acid-icobutylester, boiling point 169 ° -173 ° C./0.05 mm, are obtained «Ο s 7.4 ° (lm f chloroform).
29,3 g (0,1 Mol) D-( + )~2"-/T»(4-Chlorphenoxy)-phenoxyJr-propionsäure werden in 200 ml l'sobutylalkohol gelöst. Nach Zugabe von 0,5 ml konz. Schwefelsäure erhitzt man 15 Stunden zum Sieden, wobei über eine Kolonne das entstehende Wasser abgenommen wird.29.3 g (0.1 mol) of D (+) ~ 2 "- / T '(4-chlorophenoxy) propionic acid -phenoxyJ r are dissolved in 200 ml l'sobutylalkohol ml conc After addition of 0.5.. Sulfuric acid is heated to the boil for 15 hours, the water formed being removed via a column.
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Man destilliert anschließend das Lösungsmittel im Wasserstrahlvakuum weitgehend ab, nimmt den Rückstand in Methylenchlorid auf und wäscht mit Wasser. Nach Abdampfen des Methylenchlorids destilliert man das Produkt im Hochvakuum. Man erhält 30,1 g (86 Ji d. Th.) D-(+)-2-/?-(4-Chlorphenoxy)-phenoxyT-propionsäure-isobutylester, Sdp. 167°C/0,04 mm, aD*o = 7,5° (1 m, Chloroform).The solvent is then largely distilled off in a water jet vacuum, the residue is taken up in methylene chloride and washed with water. After the methylene chloride has been evaporated off, the product is distilled in a high vacuum. (Th 86 ji d..) D is obtained 30.1 g - (+) - 2 - / - (4-chlorophenoxy) -phenoxyT-propionic acid isobutyl ester, b.p. 167 ° C / 0.04 mm, a D. * o = 7.5 ° (1 m, chloroform).
D-(+ )-2-£Ä- (2,4-Dichlorphenoxy)-phenoxy7-propionsäure· methylesterD - (+ ) -2- £ Ä- (2,4-dichlorophenoxy) -phenoxy7-propionic acid · methyl ester
-Cl-Cl
25,5 g (0,10 Mol) 4-(2,4-Dichlorphenoxy)-phenol v/erden mit 25,8 g (0,10 Mol) L-(-)-Milchsäuremethylester-tosylat und 15t2 g (Of11 Mol) gepulvertem, wasserfreiem Kaliumcarbonat in 150 ml Acetonitril 14 Stunden zum Sieden unter Rückfluß erhitzt. 25.5 g (0.10 mol) 4- (2,4-dichlorophenoxy) phenol v / earth with 25.8 g (0.10 mol) L - (-) - lactic acid methyl ester tosylate and 15 t 2 g ( Of11 mol) of powdered, anhydrous potassium carbonate in 150 ml of acetonitrile heated to reflux for 14 hours.
Nach Erkalten wird vom Salzrückstand abfiltriert, das Lösungsmittel abgedampft und der verbleibende Rückstand im Hochvakuum destilliert.After cooling, the salt residue is filtered off, the solvent evaporated and the remaining residue distilled in a high vacuum.
Man erhält 28,1 g (82 % d. Th.) D-(+)-2-/T-(2,4-Dichlcrphenoxy)-phenoxy^-propionsäuremethylester, Sdp. 167°C/O,O3 nun, aD8° = 6f9° ^1 m* Chloroform).28.1 g (82 % of theory ) of D - (+) - 2- / T- (2,4-dichlorophenoxy) -phenoxy-3-propionic acid methyl ester, boiling point 167 ° C./0.3 now, a D ° = 8 ° 6F9 * ^ 1 m oroform Chl).
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D-(+)-2-/T-(2t4-Dichlorphenoxy)-phenoxy7-propionsäure·- äthyüester D - (+) - 2- / T- (2 t 4-dichlorophenoxy) -phenoxy x y7-propionic acid - ethyl ester
CO2C2H5 CO 2 C 2 H 5
erhe
Man suspendiert 27,7 g (0,10 Mol) trockenes Katrium-4-(2,4-Dichlorphenoxy)-phenolat in 200 ml Xylol und erhitzt die Suspension auf 1100C. Im Laufe einer halben Stunde tropft man 20,6 g (0,105 Mol) L-(-)-Milchsäureäthylester-niesylat zu und erhitzt 4 Stunden zum Sieden unter Rückfluß. Nach Erkalten trennt man vom ausgeschiedenen Salzrückstand, dampft das Lösungsmittel ab und destilliert den verbleibenden Rückstand im Hochvakuum.Is suspended 27.7 g (0.10 mol) of dry Katrium-4- (2,4-dichlorophenoxy) phenolate in 200 ml of xylene and the suspension was heated to 110 0 C. In the course of half an hour is added dropwise 20.6 g (0.105 mol) L - (-) - lactic acid ethyl ester niesylate and heated to boiling under reflux for 4 hours. After cooling, the salt residue which has separated out is separated off, the solvent is evaporated off and the residue that remains is distilled in a high vacuum.
Man erhält 17,0 g (48 f> d. Th.) D-( + )-2-/_4"-(2,4-Dichlorphenoxy)-phenoxy_7-propionsäureäthylester, Sdp. 196°C/O,O5 mm, C1J20 = 6,5° (1 D, Chloroform).17.0 g (48 f> d. Th.) D- (+) -2 - / _ 4 "- (2,4-dichlorophenoxy) -phenoxy-7-propionic acid ethyl ester, bp. 196 ° C / O, 0.5 mm, C 1 J 20 = 6.5 ° (1 D, chloroform).
10,2 g (0,040 Mol) 4-(2,4-Dichlcrphenoxy)-phenol werden mit 12,7 g (0,044 Mol) L-(-)-Milchsäureäthylester-4-methoxybenzolsulfonat und 6,6 g (0,048 Mol) gepulvertem, wasserfreiem Kaliumcarbonat in 70 ml Aceton 80 Stunden zum Sieden unter Rückfluß erhitzt.10.2 g (0.040 mol) 4- (2,4-dichlorophenoxy) -phenol are with 12.7 g (0.044 mol) of L - (-) - ethyl lactate 4-methoxybenzenesulfonate and 6.6 g (0.048 mol) of powdered, anhydrous potassium carbonate in 70 ml of acetone for 80 hours to boil Heated to reflux.
Nach Erkalten wird vom Salzrückstand abfiltriert, das Lösungsmittel abgedampft und der verbleibende Rückstand im Hochvakuum destilliert.After cooling, the salt residue is filtered off, the solvent evaporated and the remaining residue distilled in a high vacuum.
Man erhält 11,5 g (81 $ d. Th.) D-(+)"2~/?-(2,4-Dichlorphenoxy)-phenoxy7-propionsäureäthylester, Sdp. 180°C/0,03 mm, (X1*ο = 6,6° (1 m, Chloroform).This gives 11.5 g (81 $ of theory..) D - (+) "2 ~ / - (2,4-dichlorophenoxy) -phenoxy7-ethyl propionate, b.p. 180 ° C / 0.03 mm, (X. 1 * ο = 6.6 ° (1 m, chloroform).
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3,0 g (11,6 mMol) 4-(2,4-Dichlorphenoxy)-phenol werden mit 3,5 g (11,6 mMol) L-(-)-Milchsäureäthylester-4-nitrobenzolsulfonat und 1,8 g (12,7 mMol) gepulvertem, wasserfreiem Kaliumcarbonat in 40 ml Aceton 24 Stunden zum Sieden unter Rückfluß erhitzt.3.0 g (11.6 mmol) 4- (2,4-dichlorophenoxy) -phenol are with 3.5 g (11.6 mmol) of L - (-) - ethyl lactate 4-nitrobenzenesulfonate and 1.8 g (12.7 mmol) of powdered, anhydrous potassium carbonate in 40 ml of acetone to boiling for 24 hours Heated to reflux.
Nach Erkalten wird vom Salzrückstand abfiltriert, das Lösungsmittel und der verbleibende Rückstand im Hochvakuum destilliert, Man erhält 3,6 g (87 $> d. Th.) D-(+)-2-^T-(2,4-Dichlorphenoxy)-phenoxyZ-propionsaureathylester, Sdp. 197°C/O,O6 mm, O0*ο = 4,7° (0,7 m, Chloroform).After cooling, the salt residue is filtered off, the solvent and the remaining residue are distilled in a high vacuum, 3.6 g (87 $> d. Th.) D - (+) - 2- ^ T- (2,4-dichlorophenoxy) are obtained -phenoxyZ-propionic acid ethyl ester, bp. 197 ° C / O, 06 mm, O 0 * ο = 4.7 ° (0.7 m, chloroform).
Beispiel 6 A:Example 6 A:
D- (+ )-2-^T-(2.4-Dichlorphenoxy j-phenoxy^-propionsäurechlorid D- (+) -2- ^ T- (2.4-dichlorophenoxy j-phe nox y ^ -propionic acid chloride
-Cl-Cl
52,3 g (0,160 Mol) D-(+)-2-^~(2,4-DichlorphenoxyJ-phenoxyJ-propionsäure, erhalten durch Verseifung des nach Beispiel 5 erhaltenen Aethylesters analog Beispiel 2, werden in 200 ml Toluol gelöst. Nach Zugabe von 22,8 g (0,192 Mol) Thionylchlorid erhitzt man 13 Stunden zum Sieden unter Rückfluß. Durch Destillation unter vermindertem Druck destilliert man Lösungsmittel und nicht umgesetztes Thionylchlorid ab. Den Rückstand von 61,3 g nimmt man in 238,7 g Benzol auf und erhält damit eine ca. 18 %ige Lösung des D-(+)-2-/?-(2,4-Dichlorphenoxy )-phenoxy7-propionsäurechlorids, die direkt für weitere Umsetzungen verwendbar ist.52.3 g (0.160 mol) D - (+) - 2- ^ ~ (2,4-dichlorophenoxyJ-phenoxyJ-propionic acid, obtained by saponification of the ethyl ester obtained according to Example 5 analogously to Example 2, are in 200 ml Toluene dissolved. After adding 22.8 g (0.192 mol) of thionyl chloride, the mixture is refluxed for 13 hours. The solvent and unreacted thionyl chloride are distilled off by distillation under reduced pressure. The The residue of 61.3 g is taken up in 238.7 g of benzene and an approx. 18% solution of D - (+) - 2 - /? - (2,4-dichlorophenoxy is obtained ) -phenoxy7-propionic acid chloride, which is used directly for further conversions can be used.
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Beispiel 6 B;Example 6 B;
D- (+ D- (+ )-2-[K- ) -2- [K- (2.4-Dichlorphenoxy )-phenoxy_7-propionsäure-2-(2.4-dichlorophenoxy) -phenoxy_7-propionic acid-2- (methoxy)--äthy!ester(methoxy) - ethy! ester
CO2CH2CH2OCH3 CO 2 CH 2 CH 2 OCH 3
>-Cl> -Cl
85 g der in Beispiel 6 A erhaltenen benzolischen Lösung des D- (+)-2-JT- (2,4-Dichlorphenoxy )-phenoxjr7-propionsäurechlorids (ca. 45 mMol) werden bei Raumtemperatur zu einer Mischung von 3,8 g (50 mMol) Aethylenglykol-monomethyläther mit 5,1 g (50 mMol) Triäthylamin und 50 ml Benzol getropft. Man rührt 3 Stunden bei 500C nach, kühlt ab und filtriert vom ausgeschiedenen Triäthylammoniumhydrochlorid. Das Filtrat wird mit Wasser gewaschen, das Benzol abgedampft und der Rückstand durch Chromatcgraphieren an Kieselgel gereinigt. Man erhält 15,7 g (91 1° d. Th.) D-( + )~2-/4~-(2,4-Dichlorphenoxy)-phenoxy7-propionsäure-2-(methoxy)-äthylester, oCjf0 - 2,6 (0,5 π, Chloroform).85 g of the benzene solution of D- (+ ) -2-JT- (2,4-dichlorophenoxy) -phenoxjr7-propionic acid chloride obtained in Example 6 A (approx. 45 mmol) are added at room temperature to a mixture of 3.8 g ( 50 mmol) of ethylene glycol monomethyl ether with 5.1 g (50 mmol) of triethylamine and 50 ml of benzene were added dropwise. The mixture is stirred for 3 hours at 50 ° C., cooled and the triethylammonium hydrochloride which has precipitated out is filtered off. The filtrate is washed with water, the benzene is evaporated and the residue is purified by chromatography on silica gel. 15.7 g (91 1 ° of theory ) of D- (+) ~ 2- / 4 ~ - (2,4-dichlorophenoxy) phenoxy7-propionic acid 2- (methoxy) ethyl ester, oCjf 0 - are obtained 2.6 (0.5π, chloroform).
D- (-f )-2-fÄ- (2,4-Dichlorphenoxy )-yhenoxv7-propionsäure-3-(methoxy)-n-butylestcr D- (-f ) -2-fÄ- (2,4-dichlorophenoxy) -yhenoxy-7-propionic acid-3- (methoxy) -n-butyl ester
ι CH2 CH2 CH»^/·ι CH 2 CH 2 CH »^ / ·
85 g der in Beispiel 6 A erhaltenen benzolischen Lösung des D- (+)-2-/J-(2,4-Dichlorphenoxy J-phenoxy^-propionsäurechlorids (ca. 45 mMol) werden bei Raumtemperatur zu einer Mischung von 5,2 g (50 mMol) 3-Methoxy-l-butanol mit 5,1 g (50 mMol) Triäthylamin und 50 ml Benzol getropft. Man rührt 3 Stunden bei 500C nach, kühlt ab und filtriert vom ausgeschiedenen Triäthyl-85 g of the benzene solution of D- (+ ) -2- / J- (2,4-dichlorophenoxy J-phenoxy ^ -propionic acid chloride obtained in Example 6 A (approx. 45 mmol) become a mixture of 5.2 at room temperature g (50 mmol) of 3-methoxy-l-butanol with 5.1 g (50 mmol) of triethylamine and 50 ml of benzene was added dropwise. the mixture is stirred for 3 hours at 50 0 C, cooled and filtered from the precipitated triethyl
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ammonium-hydrochlorid. Das Filtrat wird mit Wasser gewaschen, das Benzol abgedampft lind der Rückstand durch Chromatographieren an Kieselgel gereinigt.ammonium hydrochloride. The filtrate is washed with water, the benzene is evaporated and the residue is chromatographed Purified on silica gel.
Man erhält 14,5 g (78 # d. Th.) D-(+)-2-/4"-(2,4-Dichlor~ phenoxy)-phenoxy_7-propionsäure-3-(methoxy)-n-butylester, aD2° = 5t°° ^0'5 m» Chloroform)· 14.5 g (78 # of theory) D - (+) - 2- / 4 "- (2,4-dichloro-phenoxy) -phenoxy-7-propionic acid 3- (methoxy) -n-butyl ester are obtained, a D 2 ° = 5t °° ^ 0 ' 5 m » chloroform ) ·
D- (+ )-2-^4- (2.4-Dichlorphenoxy )-phenoxy_7-prop.ionsäuretetrahydrofurfurylesterTetrahydrofurfuryl D- (+) -2- ^ 4- (2.4-dichlorophenoxy) -phenoxy-7-prop.ionic acid
85 g der in Beispiel 6A erhaltenen benzolischen Lösung des D- (+ )-2-/J- (2,4-Dichlorphenoxy )-phenoxy_7-propionsäurechlorids (ca, 45 mMol) v/erden bei Raumtemperatur zu einer Mischung von 5,1 g (50 mMol) Tetrahydrofurfurylalkohol mit 5,1 g (50 ir.Mol) Triäthylamin und 60 ml Benzol getropft. Man rührt 3 Stunden bei 50"C nach, kühlt ab und filtriert vom ausgeschiedenen Triäthylammonium-hydrochlorid. Das Filtrat wird mit Wasser gewaschen, das Benzol abgedampft und der Rückstand durch Chromatographieren an Kieselgel gereinigt.85 g of the benzene solution of D- (+ ) -2- / J- (2,4-dichlorophenoxy) -phenoxy-7-propionic acid chloride (approx. 45 mmol) obtained in Example 6A ground at room temperature to give a mixture of 5.1 g (50 mmol) of tetrahydrofurfuryl alcohol with 5.1 g (50 ir.Mol) of triethylamine and 60 ml of benzene were added dropwise. The mixture is stirred for 3 hours at 50 ° C., cooled and the precipitated triethylammonium hydrochloride is filtered off. The filtrate is washed with water, the benzene is evaporated off and the residue is purified by chromatography on silica gel.
Man erhält 16,2 g (88 % d. Th.) D-(+)-2-/T~(2,4-Dichlorphenoxy)· phenoxyy-propionsäure-tetrahydrofurfürylester, a^80 = 2,7° (0,5 m, Chloroform).16.2 g (88% of theory) D - (+) - 2- / T ~ (2,4-dichlorophenoxy) phenoxy-propionic acid tetrahydrofuran, a ^ 80 = 2.7 ° (0, 5 m, chloroform).
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äthylesterethyl ester
CO2C2H6 CO 2 C 2 H 6
-Br-Br
15»O g (OfO5O Mol) 4-(4-Broci-2-chlorphenoxy)-phenol v/erden mit 10,2 g (0,052 FdI) L-(~)-Milchsäureäthylester-mesylat und 7,6 g (0,055 Hol) gepulvertem, wasserfreiem Kaliumcarbonat in 100 ml Acetonitril 20 Stunden zum Sieden unter Rückfluß erhitzt. 15 »O g (O f O50 mol) 4- (4-Broci-2-chlorophenoxy) -phenol v / earth with 10.2 g (0.052 FdI) L- (~) -lactic acid ethyl ester mesylate and 7.6 g ( 0.055 Hol) powdered, anhydrous potassium carbonate in 100 ml of acetonitrile heated to boiling under reflux for 20 hours.
Nach Erkalten filtriert nan vom ausgeschiedenen Salzrückstand, dampft das Lösungsmittel ab und destilliert den verbleibenden Rückstand im Hochvakuum.After cooling down, nan filtered from the precipitated salt residue, the solvent is evaporated and the remaining residue is distilled in a high vacuum.
Man erhält 17,2 g (86 % d. Th.) D-(+)-2-/4-(4-3rom-2-chlorphenoxy)-phenoxy/-propionsäure-äthylester, Sdp. 190° - 193°C/ 0,025 mm, αβ 20 = 4,5°(1 m, Chloroform).17.2 g (86 % of theory ) of D - (+) - 2- / 4- (4-3rom-2-chlorophenoxy) phenoxy / propionic acid ethyl ester, bp 190 ° -193 ° C. are obtained / 0.025 mm, α β 20 = 4.5 ° (1 m, chloroform).
D-(-f )-2-^4-(4-Brom-2-chlor~phsnoxv )--phenoy.y7-propj.onsäure· methvlester D - (- f) -2- ^ 4- (4-bromo-2-chloro ~ p hsnoxv) -phenoy.y7-propj.onsäure · m ethvlester
CO2CH3 CO 2 CH 3
94,2 g (0,236 Mol) D-(+)-2~/?-(4-Brom-2-chlor-phenoxy)-phenoxy^-propionsäureä-thylester (vgl. Beispiel 9) werden in 700 ml Methanol gelöst. Man gibt 3 ml konzentrierte Schwefelsäure hinzu und erhitzt 8 Stunden zum Sieden unter Rückfluß. Man destilliert die entstandene Mischung von Methanol und Aethanol unter vermindertem Druck weitgehend ab, setzt erneut 700 ml Methanol hinzu und erhitzt nochmals 8 Stunden zum94.2 g (0.236 mol) of D - (+) - 2 ~ /? - (4-Bromo-2-chlorophenoxy) -phenoxy-1-propionic acid ethyl ester (see. Example 9) are dissolved in 700 ml of methanol. 3 ml of concentrated sulfuric acid are added added and heated to reflux for 8 hours. The resulting mixture of methanol and is distilled Most of the ethanol is removed under reduced pressure, another 700 ml of methanol are added and the mixture is heated again for 8 hours
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Sieden. Anschließend destilliert man das Methanol ab, nimmt den Rückstand in Chloroform auf, wäscht mit Wasser säurefrei und entfernt das Lösungsmittel durch Abdestillieren. Der verbleibende Rückstand wird im Hochvakuum fraktioniert. Man erhält als Hauptfraktion 78,6 g (86 M· Th.) D-(+)-2-ß~(4-Brom-2-chlor-phenoxyJ-phenoxyJ-propionsäuremethylester r Sdp. 173°-177°C/O,O3 mm, aD*° = 6,7° (1 m, Chloroform). Das Produkt erstarrt beim Erkalten, Fp. 51° - 54-0C. Durch Umkristallisieren aus Methanol erhält man die reine Verbindung vom Fp. 56°C, aD 20 = 8,9° (l m, Chloroform).Boil. The methanol is then distilled off, the residue is taken up in chloroform, washed acid-free with water and the solvent is removed by distillation. The remaining residue is fractionated in a high vacuum. As the main fraction D is obtained 78.6 g (86 M · Th.) - (+) - 2- ß ~ (4-bromo-2-chloro-phenoxyJ-phenoxyJ-propionate r b.p. 173 ° -177 ° C / O. , O3 mm, a * D ° = 6.7 ° (1 m, chloroform) the product solidifies on cooling, mp 51 ° -... 54- 0 C. recrystallization from methanol gives the pure compound, melting at 56 ° C, a D 20 = 8.9 ° (lm, chloroform).
D-(+)-2~/4"«-(4-Trifluormethy!phenoxy)-phenoxyy-proplonsäure· methylesterD - (+) - 2 ~ / 4 "« - (4-Trifluoromethy! Phenoxy) -phenoxyy-proplonic acid · methyl ester
HlSt.
25,4 g (0,10 Mol) 4-(4-Trifluormethylphenoxy)phenol werden mit 28,4 g (0,11 Mol) L-(-)-Milchsäuremethylester-tosylat und 16,6 g (0,12 Mol) gepulvertem, wasserfreiem Kaliumcarbonat in 150 rol Acetonitril 15 Stunden zum Sieden unter Rückfluß erhitzt, Nach Erkalten filtriert man vom ausgeschiedenen Salzrückstand, dampft das Lösungsmittel ab und destilliert den verbleibenden Rückstand im Hochvakuum.25.4 g (0.10 moles) of 4- (4-trifluoromethylphenoxy) phenol become with 28.4 g (0.11 mol) of L - (-) - lactic acid methyl ester tosylate and 16.6 g (0.12 mol) of powdered, anhydrous potassium carbonate in 150 rol of acetonitrile heated to boiling under reflux for 15 hours, After cooling, the precipitated salt residue is filtered off, the solvent is evaporated off and the remaining residue is distilled Residue in a high vacuum.
Man erhält 30,6 g (90 # d. Th.) D-(+)-2-/T-(4-Trifluormethylphenoxy)-phenoxy.7-propionsäure-methylester, Sdp· 157° - 159°C/ 0,04 mm, aD*o = 7,0° (1 n, Chloroform).30.6 g (90 # of theory) of D - (+) - 2- / T- (4-trifluoromethylphenoxy) phenoxy.7-propionic acid methyl ester, bp 157 ° - 159 ° C./0, are obtained 04 mm, a D * o = 7.0 ° (1N, chloroform).
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D-(-f )-2-^T»(4-Trifluormethylphenoxy)-phenox^7-propionsäure äthylester D - (- f) -2- ^ T »(4-trifluoromethylphenoxy) -phenox ^ 7-propionic acid, ethyl ester
CO2C2H6 CO 2 C 2 H 6
152,4 g (0,6 Mol) 4-(4~Trifluormethylphenoxy)-phenol werden mit 179,5 g (0,66 Mol) !/-(O-Milchsäureäthylester-tosylat und 95»2 g (0,69 Mol) gepulvertem, wasserfreiem Kaliumcarbonat in 1000 ml Aceton 72 Stunden zum Sieden unter Rückfluß erhitzt.152.4 g (0.6 mol) of 4- (4 ~ trifluoromethylphenoxy) phenol with 179.5 g (0.66 mol)! / - (O-lactic acid ethyl ester tosylate and 95 »2 g (0.69 mol) of powdered, anhydrous potassium carbonate in 1000 ml of acetone heated to reflux for 72 hours.
Nach Erkalten filtriert man vom ausgeschiedenen Salzrückstand, dampft das Lösungsmittel ab und destilliert den verbleibenden Rückstand im Hochvakuum.After cooling down, the precipitated salt residue is filtered off, the solvent is evaporated and the remaining residue is distilled in a high vacuum.
Man erhält 206 g (97 "/-> d. Th4) D-(-h)-2-/4--(4-Trifluormethylphenoxy)-phenoxy7-propionsäure-äthylester, Sdp. 150° - 156°C/ 0,05 mm, a^-° = 5,0° (1 m, Chloroform).206 g (97 "/ -> d. Th 4 ) D - (- h) -2- / 4 - (4-trifluoromethylphenoxy) -phenoxy7-propionic acid ethyl ester, bp 150-156 ° C./0 are obtained .05 mm, a ^ - ° = 5.0 ° (1 m, chloroform).
Das Produkt erstarrt beim Erkalten, Fp. 58°-64°C.The product solidifies on cooling, melting point 58 ° -64 ° C.
Durch Umkristallisieren aus Aethanol erhält man die reine Verbindung vom Fp. 68,.50C, oc^20 = 9,3° (l in, Chloroform).Recrystallization from ethanol gives the pure compound, mp. 68 C 0 .5, oc ^ 20 = 9.3 ° (l in, chloroform).
Beispiel 13:Example 13:
D- (+ )-2-/J- (2,4;-pichlprbenzyl )-phencxy_7-propionsäureäthylester D- (+ ) -2- / J- (2,4 ; -pichl prbenzyl) -phenoxy-7-propionic acid ethyl ester
CO2C2H5 CO 2 C 2 H 5
38,0 g (0,150 Mol) 4-(2,4-Dichlorbenzyl)-phenol werden mit 44,9 g (0,165 Mol) L-(-)-Milchsäureäthylester-tosylat und 24,8 g (0,180 Mol) gepulvertem, wasserfreiem Kaliumcarbonat in 200 ml Acetonitril 22 Stunden zum Sieden unter Rückfluß erhitzt.38.0 g (0.150 mol) of 4- (2,4-dichlorobenzyl) phenol are tosylate with 44.9 g (0.165 mol) of L - (-) - lactic acid ethyl ester and 24.8 g (0.180 mol) of powdered, anhydrous potassium carbonate in 200 ml of acetonitrile at reflux for 22 hours heated.
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Nach Erkalten wird vom Salzrückstand abfiltriert, das Lösungsmittel abgedampft und der verbleibende Rückstand im Hochvakuum destilliert.After cooling, the salt residue is filtered off, the solvent evaporated and the remaining residue distilled in a high vacuum.
Man erhält 36,7 g (69 % d. Th.) D-(+)-2-/4-(2,4-Dichlorbenzyl)-phenoxy/-propionsäureäthylester, Sdp. 16O°C/O,O2 mm? aD2° = ^>0° ^1 m» Chloroform).36.7 g (69 % of theory ) of D - (+) - 2- / 4- (2,4-dichlorobenzyl) phenoxy / propionic acid ethyl ester, boiling point 160 ° C./0.2 mm? a D 2 ° = ^ > 0 ° ^ 1 m »chloroform).
Beispiel 14:Example 14:
methylestermethyl ester
CO2CH3 CO 2 CH 3
22,8 g (0,062 Mol) D-(+)-2-/T-(2,4-Dichlorbenzyl)-phenoxv7-propionsäureäthy!ester (vgl. Beispiel 13) werden in 1600 ml Methanol gelöst. Man gibt 3 ml konzentrierte Schwefe!säure hinzu und erhitzt 30 Stunden zum Siecen unter Rückfluß. Anschließend destilliert man das Methanol ab, nimmt den Rückstand in Chloroform auf, wäscht mit Wasser säurefrei und entfernt das Lösungsmittel durch Abdestillieren. Der verbleibende Rückstand wird im Hochyakkuum fraktioniert. Man erhält 19,9 g (90 % d. Th.) D-(+)-2-/ϊ-(2,4-Dichlorbenzyl)-phenoxy^-prcpionsäuremethylester, Sdp. 180°C/0,15 mm, aD2° = ^>6° ^1 m» Chloroform).22.8 g (0.062 mol) of D - (+) - 2- / T- (2,4-dichlorobenzyl) -phenoxv7-propionic acid ethyl ester (cf. Example 13) are dissolved in 1600 ml of methanol. 3 ml of concentrated sulfuric acid are added and the mixture is refluxed for 30 hours to sift. The methanol is then distilled off, the residue is taken up in chloroform, washed acid-free with water and the solvent is removed by distillation. The remaining residue is fractionated in a high vacuum. 19.9 g (90 % of theory ) of D - (+) - 2- / ϊ- (2,4-dichlorobenzyl) phenoxy ^ -prcpionic acid methyl ester, bp. 180 ° C / 0.15 mm, a D 2 ° = ^ > 6 ° ^ 1 m »chloroform).
Beispiel 15:Example 15:
]> (+ )-2-ffi- (f)-Chlor-2-benzoxazolyloxy)-pb enoxy7-prop lon säure ■ äthylester ] > (+) -2-ffi- (f) -Chlor-2-benzoxazolyloxy) -pb enoxy7-propionic acid ■ ethyl ester
HlSt.
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26,2 g (0,1 Mol) 4-(5-Chlor-2-benzoxazolyloxy)-phenol werden mit 16,6 g (0,12 Mol) Kaliumcarbonat in 120 ml Acetonitril 1 1/2 Stunden zum Sieden erhitzt, anschließend werden 29,9 g (0,11 Mol) L-(-)-Milchsäureäthylester-tosylat, gelöst in 50 ml Acetonitril innerhalb von 15 Minuten zugetropft. Das Reaktions~ gemisch v/ird nach der Zugabe 12 Stunden am Sieden gehalten, der Salzanteil wird abfiltriert und vom Filtrat Acetonitril abdestilliert. Der verbleibende Rückstand wird in 200 ml Methylerchlorid aufgenommen, zweimal mit je 100 ml Wasser gewaschen, nach Trocknen über Natriumsulfat wird Methylenchloi'id abdestilliert. Der erhaltene Rückstand v/ird destilliert. Nach der Destillation erhält man 29,8 g (82,5 % d. Th.) an überwiegend D-(+) enthaltendem 2~/4*-(5-Chlor-2-benzoxazolyloxy)-phenoxy_7-propionsäureäthylester mit Fp. 53°-550C und an 2c = 11,3° (1 m, Chloroform).26.2 g (0.1 mol) 4- (5-chloro-2-benzoxazolyloxy) phenol are heated to the boil for 1 1/2 hours with 16.6 g (0.12 mol) potassium carbonate in 120 ml acetonitrile, then 29.9 g (0.11 mol) of L - (-) - ethyl lactate tosylate, dissolved in 50 ml of acetonitrile, are added dropwise over the course of 15 minutes. The reaction mixture is kept boiling for 12 hours after the addition, the salt fraction is filtered off and acetonitrile is distilled off from the filtrate. The remaining residue is taken up in 200 ml of methylene chloride, washed twice with 100 ml of water each time, and after drying over sodium sulfate, methylene chloride is distilled off. The residue obtained is distilled. After the distillation, 29.8 g (82.5 % of theory ) of 2 ~ / 4 * - (5-chloro-2-benzoxazolyloxy) -phenoxy-7-propionic acid ethyl ester with a melting point of 53 are obtained -55 ° C 0 and a n 2c = 11.3 ° (1 m, chloroform).
Beispiel 16;Example 16;
D-(f )-2-^T~(6-Chlor-2-benzthiazolyloxy )~phenoxy_7-propionsäure· äthylester D- (f) -2- ^ T ~ (6-chloro-2-benzthiazolyloxy) ~ phenoxy_ 7-propionic acid ethyl ester
27,8 g (0,1 Mol) 4-(6-Chlor-2-benzthiazolyloxy)-phenol werden mit 16,6 g (0,12 Mol) Kaliumcarbonat in 120 ml Acetonitril 1 1/2 Stunden zum Sieden erhitzt. Anschließend werden 29,9 g (0,11 Mol) L-(-)-Milchsäureäthylester-tosylat, gelöst in 50 ml Acetonitril, innerhalb von 15 Minuten zugetropft. Das Reaktionsgemisch wird nach der Zugabe 5 Stunden am Sieden gehalten, der Salzanteil wird abfiltriert und vom Filtrat Acetonitril abdestilliert. Der verbleibende Rückstand wird in 200 ml Methylenchlorid aufgenommen, zweimal mit Je 100 ml Wasser ge-27.8 g (0.1 mol) of 4- (6-chloro-2-benzthiazolyloxy) phenol are mixed with 16.6 g (0.12 mol) of potassium carbonate in 120 ml of acetonitrile Heated to the boil for 1 1/2 hours. Then 29.9 g (0.11 mol) of L - (-) - ethyl lactate tosylate, dissolved in 50 ml Acetonitrile, added dropwise within 15 minutes. After the addition, the reaction mixture is kept boiling for 5 hours, the salt fraction is filtered off and acetonitrile is distilled off from the filtrate. The remaining residue is in 200 ml Added methylene chloride, twice with 100 ml of water each
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waschen, nach Trocknen über Natriumsulfat wird Methylenchlorid abdestilliert. Der erhaltene Rückstand wird destilliert. Nach der Destillation erhält man 34,5 g (91,4 % d. Th.) an überwiegend D-(+) enthaltendem 2-/?-(6-Chlor-2-benzthiazolyloxy)-phenoxyT-propionsäureäthylester mit Fp. 49°C und αβ 20 = 9,5° (Im, Chloroform).wash, after drying over sodium sulfate, methylene chloride is distilled off. The residue obtained is distilled. After the distillation, 34.5 g (91.4 % of theory ) of 2 - /? - (6-chloro-2-benzthiazolyloxy) -phenoxyT-propionic acid ethyl ester with a melting point of 49 ° are obtained, mainly containing D - (+) C and α β 20 = 9.5 ° (Im, chloroform).
Nach Umkristallisieren aus einem Aethanol/Wasser-Gemisch wird das Produkt optisch reiner und hat dann Fp. 51°C und aD*° = 11° (1 m, Chloform).After recrystallization from an ethanol / water mixture, the product is optically purer and then has a melting point of 51 ° C. and a D * ° = 11 ° (1 m, chloroform).
D-( + )-2-/T-( 3, 5~Dichlor-2-pyr idyl oxy )~phenoxv7-propionsäure äthylester D- (+) -2- / T- (3, 5 ~ dichloro-2-pyridyl oxy) ~ ph enoxv7-propionic acid, ethyl ester
CH3 CH 3
H5 C2 0OC ► C ^ 0-H H 5 C 2 0OC ► C ^ 0 - H
19,7 g (0,077 Mol) 4-(3,5-Dichlor~2-pyridyioxy)-phenol v/erden mit 12,7 g (0,092 Mol) Kaliumcarbonat (wasserfrei) in 150 ml Acetonitril zum Sieden erhitzt. Anschließend tropft man innerhalb von 5 Minuten 23 g (0,085 Mol) L~(-)-Milchsäureäthylestertosylat, gelöst in 50 ml Acetonitril, zu. Nach der Zugebe wird das Reaktionsgemisch 18 Stunden unter Sieden gehalten. Man kühlt ab, saugt vom Salzanteil ab und destilliert vom Filtrat Acetonitril ab. Der verbleibende ölige Rückstand wird in 200 ml Toluol aufgenommen und zweimal mit je 100 ml Wasser gewaschen· Nach Trocknen über Natriumsulfat wird Toluol abdestilliert und der vei'bleibende Rückstand destilliert. Nach der Destillation erhält man 24,8 g (90,4 # d. Th.) D~(+)-2-/T-(3,5-Dichlor-2-pyridyloxy)-phenoxv7-propionsäureäthylester mit Sdpo,ol: 174° - 176°C und aD*° = 9,7° (1 o, Chloroform).19.7 g (0.077 mol) 4- (3,5-dichloro-2-pyridyioxy) -phenol are heated to boiling with 12.7 g (0.092 mol) potassium carbonate (anhydrous) in 150 ml acetonitrile. Then, within 5 minutes, 23 g (0.085 mol) of L ~ (-) - lactic acid ethyl ester tosylate, dissolved in 50 ml of acetonitrile, are added dropwise. After the addition, the reaction mixture is kept boiling for 18 hours. It is cooled, the salt content is filtered off with suction and acetonitrile is distilled off from the filtrate. The remaining oily residue is taken up in 200 ml of toluene and washed twice with 100 ml of water each time. After drying over sodium sulfate, toluene is distilled off and the remaining residue is distilled. After the distillation, 24.8 g (90.4 # of theory) of D ~ (+) - 2- / T- (3,5-dichloro-2-pyridyloxy) -phenoxv7-propionic acid ethyl ester with boiling point o , ol : 174 ° - 176 ° C and a D * ° = 9.7 ° (10, chloroform).
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- 28 -- 28 -
BIOLOGISCHE BEISPIELEBIOLOGICAL EXAMPLES
Die optisch aktiven D-(+)-Verbindungen (im einzelnen s. Tabellen) wurden in Freilandversuchen im Vergleich zu den entsprechenden Racematen im Nachauflaufverfahren gegen verschiedene Schadgräser geprüft. Die Parzellengrößen lagen bei 5 bzw. 10m2; es wurde mit 3- bis 4-facher Wiederholung gearbeitet. Die Verbindungen wurden als Emulsionskonzentrate formuliert und in verschiedenen Aufwandmengen je ha bei einem Wasseraufwand von 500 l/ha ausgebracht, wobei die Flüssigkeitsmenge, auf 1 ha bezogen, jeweils 500 1 betrug. The optically active D - (+) - compounds (for details see tables) were tested in field tests in comparison with the corresponding racemates in the post-emergence method against various grass weeds. The parcel sizes were 5 and 10m 2 ; it was worked with 3 to 4 times repetition. The compounds were formulated as emulsion concentrates and applied in various application rates per ha with a water rate of 500 l / ha, the amount of liquid, based on 1 ha, being 500 l in each case.
Die Wirksamkeit der Produkte wurde 30 - 35 Tage nach der Behandlung mittels "BBA-Schema 1-9" (Biologische Bundesanstalt, Braunschweig) festgestellt, wobei 1 eine 100 %ige Wirkung und 9 keinerlei Wirkung bedeutet. Bei den Kulturpflanzen bedeutet 1 keine Schädigung und 9 eine totale Schädigung der Pflanzen. Die Kulturpflanzenverträglichkeit wurde außerdem zum ersten Mal bereits eine Woche nach der Behandlung bonitiert.The effectiveness of the products was 30-35 days after treatment using "BBA scheme 1-9" (Biological Federal Institute, Braunschweig) determined, with 1 being 100% effective and 9 means no effect. In the case of cultivated plants, means 1 no damage and 9 total damage to the plants. The crop plant tolerance was also to rated for the first time a week after the treatment.
Die in der Tabelle angegebenenThe ones given in the table
;-- bzw. EDgg-Werte geben an,; - or EDgg values indicate
bei welcher Wirkstoffdosis/ha 95 % bzw. 98 % der Schadpflanzen abgetötet werden (ED ="effective dose")at what dose of active ingredient / ha 95% or 98% of the harmful plants be killed (ED = "effective dose")
Bekämpfung von Ackerfuchsschwanz: (Alopecurus mysuroides) in Zuckerrüben im Nachauflaufverfahren.Control of black foxtail: (Alopecurus mysuroides) in Post-emergence sugar beet.
Zum Zeitpunkt der Behandlung befanden sich die Zuckerrüben im 6 - 8 Blatt-Stadium. Die ED-Werte sind in Tabelle I angegeben,At the time of treatment, the sugar beets were in the 6-8 leaf stage. The ED values are given in Table I,
Beispiel (3)
kg/ha ASConnection off
Example (3)
kg / ha AS
kg/ha ASRacemate
kg / ha AS
Verbindung : Racemat Application rate
Compound: racemate
0,66 0.44
0.66
1 ,100.76
1, 10
1 :'1,67 1: 1.73
1 : '1.67
ED98 ED 95
ED 98
909827/0199909827/0199
Die Wirkstoffeinsparung liegt somit bei 40 bzw. 43 % im Vergleich zum Racemat. An den behandelten Zuckerrüben trat zu keinem Zeitpunkt Phytotoxis auf.The active ingredient savings are thus 40 or 43% compared to the racemate. On the treated sugar beets occurred Phytotoxis at no point in time.
Bekämpfung von Kühnerhirse (Echinochloa crus galli) in Zuckerrüben (4 - 6 - Blattstadium) im Nachauflaufverfahren (Ergebnis siehe Tabelle II):Control of barren millet (Echinochloa crus galli) in sugar beet (4-6 leaf stage) post-emergence (Result see table II):
Beispiel (3)
kg/ha ASConnection off
Example (3)
kg / ha AS
kg/ha ASRacemate
kg / ha AS
0,340.16
0.34
0,550.27
0.55
Verbindung : RacematApplication rate
Compound: racemate
ED98ED 95
ED 98
1 : 1,621: 1.69
1: 1.62
Die Einsparung an Wirkstoff bei gleichem Bekämpfungserfolg beträgt somit im Vergleich zum Racemat 38 bzw. 41 %. An der Zuckerrübe trat kein Kulturschaden auf.The saving in active ingredient with the same control success is thus 38 and 41% in comparison to the racemate. No crop damage occurred on the sugar beet.
Bekämpfung von Flughafer (Avena fatua) und Ackerfuchsschwanz (Alopecurus mysuroides) in Zuckerrüben (6-Blattstadium) im Nachauflaufverfahren (Ergebnis siehe Tabelle III)Control of wild oats (Avena fatua) and black foxtail (Alopecurus mysuroides) in sugar beets (6-leaf stage) in Post-emergence method (result see Table III)
Beispiel (10)
kg/ha ASConnection off
Example (10)
kg / ha AS
ka/ha ASRacemate
ka / ha AS
Verbindung : RacematApplication rate
Compound: racemate
0,520.44
0.52
0,950.80
0.95
1 : 1,831: 1.82
1: 1.83
Avena f.
ED98
AlopecurusED 95
Avena f.
ED 98
Alopecurus
Die Einsparung an Wirkstoff bei gleichem Bekämpfungserfolg beträgt somit im Verhältnis zum Racemat 45 %. An der Kulturpflanze trat keine Phytotoxis auf.The saving in active ingredient with the same control success is therefore 45% in relation to the racemate. On the cultivated plant no phytotoxis occurred.
909827/0199909827/0199
Bekämpfung von Flughafer und Ackerfuchsschwanz in Zuckerrüben (6-Blattstadium) im Nachauflaufverfahren (Ergebnis siehe Tabelle IV).Control of wild oats and field foxtail in sugar beet (6-leaf stage) post-emergence (result see Table IV).
Beispiel (11)
kg/ha ASConnection off
Example (11)
kg / ha AS
ka/ha ASRacemate
ka / ha AS
Verbindung : RacematApplication rate
Compound: racemate
0,250.15
0.25
0,420.32
0.42
1 : 1,681: 2.14
1: 1.68
ED95
ED98Alopecurus
ED 95
ED 98
0,250.21
0.25
0,650.55
0.65
1 : 2,601: 2.62
1: 2.60
ED95
ED98Avena f.
ED 95
ED 98
Die Wirkstoffeinsparung bei der Ackerfuchsschwanzbekämpfung beträgt somit im Verhältnis zum Racemat 41 bzw. 53 %. Bei Flughafer beträgt die Einsparung 62 %.The savings in active ingredients in foxtail control is therefore 41 or 53% in relation to the racemate. In the case of flying oats, the saving is 62%.
Setzt man unter gleichen Bedingungen den Aethylester aus Beispiel (1) ein, so beträgt die Wirkstoffeinsparung etwa 43 %,If the ethyl ester from example (1) is used under the same conditions, the active ingredient saving is about 43%,
Bekämpfung von Flughafer in Sommerweizen im Nachauflaufverfahren (Ergebnis siehe Tabelle V).Post-emergence control of wild oats in spring wheat (See table V for the result).
kg/ha ASRacemate
kg / ha AS
Beispiel (4)
kg/ha ASConnection off,
Example (4)
kg / ha AS
Die Wirkstoffeinsparung beträgt somit 41 % im Vergleich zum Racemat bei gleich hohem Bekämpfungserfolg. An Sommerweizen trat kein Kulturschaden auf.The active ingredient saving is thus 41% compared to Racemate with the same high level of control success. No crop damage occurred on spring wheat.
909827/0199909827/0199
Claims (4)
Phenyl, das gegebenenfalls ein- bis dreifach durch (C1-C4)-Alkyl, (C1-C4J-AIkOXy, Halogen, NO3 oder CF3 substituiert ist,(C 3 -C -) - alkynyl, which is optionally substituted once or twice by (Cj-C 6 ) -alkyl, phenyl, halogen or (C 1 -C 2 J-AlkOXy),
Phenyl, which is optionally substituted one to three times by (C 1 -C 4 ) -alkyl, (C 1 -C 4 J-AlkOXy, halogen, NO 3 or CF 3 ,
Priority Applications (36)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19772758002 DE2758002A1 (en) | 1976-09-10 | 1977-12-24 | Optically active phenoxy-propionic acid derivs. - which are more powerful herbicides than corresp. racemate |
CH829/78A CH650493A5 (en) | 1977-12-24 | 1978-01-25 | D-(+)-alpha-phenoxypropionic acid derivatives |
MX787608U MX5673E (en) | 1977-12-24 | 1978-12-15 | IMPROVED PROCEDURE FOR THE PREPARATION OF ACID DERIVATIVES D- (ALPHA-PHENOXIPROPIONICO) |
ES476100A ES476100A1 (en) | 1977-12-24 | 1978-12-18 | Optically active alpha-phenoxypropionic acid dervatives. |
BG7841786A BG33581A3 (en) | 1977-12-24 | 1978-12-19 | Herbicide means |
DE7878101792T DE2861428D1 (en) | 1977-12-24 | 1978-12-20 | Optically active compounds, process for their preparation, and their application in the protection of plants |
US05/971,427 US4531969A (en) | 1977-12-24 | 1978-12-20 | Herbicidal esters of D-1-(phenoxy-4-phenoxy)propionic acid |
EP78101792A EP0002800B2 (en) | 1977-12-24 | 1978-12-20 | Optically active alpha-phenoxypropionic acid dervatives |
NZ189267A NZ189267A (en) | 1977-12-24 | 1978-12-21 | D-(alpha-phenoxy)-propionic acid derivatives and herbicidal compositions |
ZA00787210A ZA787210B (en) | 1977-12-24 | 1978-12-21 | Optically active herbicides |
IE2547/78A IE47703B1 (en) | 1977-12-24 | 1978-12-21 | Optically active herbicidal agents |
CS788850A CS204959B2 (en) | 1977-12-24 | 1978-12-22 | Herbicide means and method of making the active component |
HU78HO2126A HU182883B (en) | 1977-12-24 | 1978-12-22 | Herbicide composition containing d-/alpha-phenoxy-propionic acid/ derivatives and process for preparing the active substances |
DD78210128A DD141403A5 (en) | 1977-12-24 | 1978-12-22 | HERBICIDE MEDIUM |
AT0921278A AT368357B (en) | 1977-12-24 | 1978-12-22 | HERBICIDAL AGENTS |
PT68979A PT68979A (en) | 1977-12-24 | 1978-12-22 | OPTICALLY ACTIVE HERBICIDES MEDIUM |
CA000318525A CA1268475A (en) | 1977-12-24 | 1978-12-22 | Optically active herbicides |
IL56283A IL56283A (en) | 1977-12-24 | 1978-12-22 | Optically active 2-(p-aryloxy-or benzylphenoxy)propionic acid derivatives,their preparation and herbicidal compositions containing them |
GR57976A GR65233B (en) | 1977-12-24 | 1978-12-22 | Active visual pesticides means |
RO7899034A RO79065A (en) | 1977-12-24 | 1978-12-22 | PROCESS FOR PREPARING D (K-PENOXYPROPIONIC) DERIVATIVES |
BR7808443A BR7808443A (en) | 1977-12-24 | 1978-12-22 | COMPOUNDS, PROCESS FOR THEIR PRODUCTION, HERBICIDAL AGENTS, AND APPLICATION OF THOSE COMPOUNDS |
DK579078AA DK156511C (en) | 1977-12-24 | 1978-12-22 | Optically active, p-substituted alpha-phenoxy-propionic acid derivatives, used as herbicides |
OA56694A OA06138A (en) | 1977-12-24 | 1978-12-22 | Optically active aryloxy-propionic acid derivatives, usable as herbicides. |
RO96022A RO75478B (en) | 1977-12-24 | 1978-12-22 | Process for preparing some derivatives of alpha-phenoxypropionic acid |
AU42849/78A AU527127B2 (en) | 1977-12-24 | 1978-12-22 | D-(alpha-phenoxy)-prodionic acid derivatives |
SU782700051A SU1336939A3 (en) | 1977-12-24 | 1978-12-22 | Herbicide |
PL1978212111A PL122180B1 (en) | 1977-12-24 | 1978-12-23 | Pesticide |
JP15817978A JPS54112828A (en) | 1977-12-24 | 1978-12-23 | Dd*alphaaphenoxy**propionic acid derivative* its maunfacture and herbicide containing it as active component |
GB7902307A GB2042503A (en) | 1977-12-24 | 1979-01-22 | Optically active herbicides |
FR7901604A FR2447366A1 (en) | 1977-12-24 | 1979-01-23 | Optically active phenoxy-propionic acid derivs. - which are more powerful herbicides than corresp. racemate |
BE193191A BE873844A (en) | 1977-12-24 | 1979-01-31 | OPTICALLY ACTIVE ARYLOXY-PROPIONIC ACID DERIVATIVES, USABLE AS HERBICIDES |
SU813233698A SU1075969A3 (en) | 1977-12-24 | 1981-01-20 | Process for preparing derivatives of d-2-(4-phenoxy)-propionic acid |
MX667383A MX6673A (en) | 1977-12-24 | 1983-03-25 | AN IMPROVED PROCEDURE FOR THE OBTAINING OF ACID DERIVATIVES D- (ALPHA-PHENOXIPROPIONICO). |
JP62251741A JPS63211250A (en) | 1977-12-24 | 1987-10-07 | D-(alpha-phenoxy)-propionic acid derivative, manufacture and herbicide |
US07/790,128 US5254527A (en) | 1977-12-24 | 1991-11-07 | Optically active herbicidal ethyl-2-(4-(6-chloro-benzoxazol-2-yloxy)-phenoxy)-propionate |
US08/465,889 US5712226A (en) | 1977-12-24 | 1995-06-06 | Optically active D-pyridyloxy phenoxy propionate herbicides |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE2640730A DE2640730C2 (en) | 1976-09-10 | 1976-09-10 | Benzoxazolyloxy and benzothiazolyloxyphenoxy compounds and herbicidal agents containing them |
DE19772758002 DE2758002A1 (en) | 1976-09-10 | 1977-12-24 | Optically active phenoxy-propionic acid derivs. - which are more powerful herbicides than corresp. racemate |
Publications (1)
Publication Number | Publication Date |
---|---|
DE2758002A1 true DE2758002A1 (en) | 1979-07-05 |
Family
ID=37075952
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
DE19772758002 Withdrawn DE2758002A1 (en) | 1976-09-10 | 1977-12-24 | Optically active phenoxy-propionic acid derivs. - which are more powerful herbicides than corresp. racemate |
Country Status (1)
Country | Link |
---|---|
DE (1) | DE2758002A1 (en) |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3018003A1 (en) * | 1979-04-09 | 1981-10-15 | Hoechst Ag, 6000 Frankfurt | Herbicide and plant growth regulant phenoxy-propionic acid ester cpds. - e.g. 2-p-6-chloro-2-benzo:thiazolyl:oxy-phenoxy-propionic acid acetone oxime ester, used against grassy weeds |
US4300944A (en) | 1978-01-18 | 1981-11-17 | Ciba-Geigy Corporation | Herbicidally active unsaturated esters of halogenated α-[4-(pyridyl-2'-oxy)-phenoxy]-propionic acids |
EP0043573A1 (en) * | 1980-07-09 | 1982-01-13 | Hoechst Aktiengesellschaft | Process for the preparation of 2,6-dichlorobenzoxazole or 2,6-dichlorobenzthiazole |
EP0044497A2 (en) * | 1980-07-19 | 1982-01-27 | Hoechst Aktiengesellschaft | Process for the production of heterocyclic substituted derivatives of 4-oxyphenoxy-alkane-carbonic acid |
EP0095115A1 (en) * | 1982-05-26 | 1983-11-30 | Bayer Ag | Substituted diphenyl ethers |
DE3219789A1 (en) | 1982-05-26 | 1983-12-01 | Bayer Ag, 5090 Leverkusen | PHENOXYPROPIONIC ACID DERIVATIVES, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS HERBICIDES |
EP0115823A1 (en) * | 1983-02-08 | 1984-08-15 | Bayer Ag | Derivatives of substituted alkane thiocarbonic acids |
EP0126361A1 (en) * | 1983-05-20 | 1984-11-28 | Bayer Ag | Optically active propionic-acid derivatives |
-
1977
- 1977-12-24 DE DE19772758002 patent/DE2758002A1/en not_active Withdrawn
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4300944A (en) | 1978-01-18 | 1981-11-17 | Ciba-Geigy Corporation | Herbicidally active unsaturated esters of halogenated α-[4-(pyridyl-2'-oxy)-phenoxy]-propionic acids |
DE3018003A1 (en) * | 1979-04-09 | 1981-10-15 | Hoechst Ag, 6000 Frankfurt | Herbicide and plant growth regulant phenoxy-propionic acid ester cpds. - e.g. 2-p-6-chloro-2-benzo:thiazolyl:oxy-phenoxy-propionic acid acetone oxime ester, used against grassy weeds |
EP0043573A1 (en) * | 1980-07-09 | 1982-01-13 | Hoechst Aktiengesellschaft | Process for the preparation of 2,6-dichlorobenzoxazole or 2,6-dichlorobenzthiazole |
EP0044497A2 (en) * | 1980-07-19 | 1982-01-27 | Hoechst Aktiengesellschaft | Process for the production of heterocyclic substituted derivatives of 4-oxyphenoxy-alkane-carbonic acid |
EP0044497A3 (en) * | 1980-07-19 | 1982-04-07 | Hoechst Aktiengesellschaft | Process for the production of heterocyclic substituted derivatives of 4-oxyphenoxy-alkane-carbonic acid |
EP0095115A1 (en) * | 1982-05-26 | 1983-11-30 | Bayer Ag | Substituted diphenyl ethers |
DE3219789A1 (en) | 1982-05-26 | 1983-12-01 | Bayer Ag, 5090 Leverkusen | PHENOXYPROPIONIC ACID DERIVATIVES, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS HERBICIDES |
EP0115823A1 (en) * | 1983-02-08 | 1984-08-15 | Bayer Ag | Derivatives of substituted alkane thiocarbonic acids |
US4599106A (en) * | 1983-02-08 | 1986-07-08 | Bayer Aktiengesellschaft | Substituted alkanethiocarboxylic acid derivatives and herbicidal use thereof |
EP0126361A1 (en) * | 1983-05-20 | 1984-11-28 | Bayer Ag | Optically active propionic-acid derivatives |
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