DE1917534A1 - 1-Aza-cycloalkene- (2,3) -1-carboxylic acid ethiol ester - Google Patents
1-Aza-cycloalkene- (2,3) -1-carboxylic acid ethiol esterInfo
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- DE1917534A1 DE1917534A1 DE19691917534 DE1917534A DE1917534A1 DE 1917534 A1 DE1917534 A1 DE 1917534A1 DE 19691917534 DE19691917534 DE 19691917534 DE 1917534 A DE1917534 A DE 1917534A DE 1917534 A1 DE1917534 A1 DE 1917534A1
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- aza
- carboxylic acid
- ester
- chloro
- cycloalkene
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D223/00—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom
- C07D223/02—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom not condensed with other rings
- C07D223/06—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom not condensed with other rings 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
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- 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
- 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
- A01N47/08—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 the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
- A01N47/16—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof the nitrogen atom being part of a heterocyclic ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D227/00—Heterocyclic compounds containing rings having one nitrogen atom as the only ring hetero atom, according to more than one of groups C07D203/00 - C07D225/00
- C07D227/02—Heterocyclic compounds containing rings having one nitrogen atom as the only ring hetero atom, according to more than one of groups C07D203/00 - C07D225/00 with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D227/04—Heterocyclic compounds containing rings having one nitrogen atom as the only ring hetero atom, according to more than one of groups C07D203/00 - C07D225/00 with only hydrogen or carbon atoms directly attached to the ring nitrogen atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, attached to ring carbon atoms
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F24—HEATING; RANGES; VENTILATING
- F24H—FLUID HEATERS, e.g. WATER OR AIR HEATERS, HAVING HEAT-GENERATING MEANS, e.g. HEAT PUMPS, IN GENERAL
- F24H1/00—Water heaters, e.g. boilers, continuous-flow heaters or water-storage heaters
- F24H1/22—Water heaters other than continuous-flow or water-storage heaters, e.g. water heaters for central heating
- F24H1/24—Water heaters other than continuous-flow or water-storage heaters, e.g. water heaters for central heating with water mantle surrounding the combustion chamber or chambers
- F24H1/26—Water heaters other than continuous-flow or water-storage heaters, e.g. water heaters for central heating with water mantle surrounding the combustion chamber or chambers the water mantle forming an integral body
- F24H1/28—Water heaters other than continuous-flow or water-storage heaters, e.g. water heaters for central heating with water mantle surrounding the combustion chamber or chambers the water mantle forming an integral body including one or more furnace or fire tubes
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F24—HEATING; RANGES; VENTILATING
- F24H—FLUID HEATERS, e.g. WATER OR AIR HEATERS, HAVING HEAT-GENERATING MEANS, e.g. HEAT PUMPS, IN GENERAL
- F24H9/00—Details
- F24H9/18—Arrangement or mounting of grates or heating means
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Combustion & Propulsion (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
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- Environmental Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Description
Badische Anilin- & Soda-Pabrik AG 1917534Badische Anilin- & Soda-Pabrik AG 1917534
Unser Zeichen: Q.Z. 26 123 Schs/KmOur reference: Q.Z. 26 123 Schs / km
6700 Ludwigshafen, 3. April 1969 · l-Aza-cycloalken-(2,3)-l-carbonsäurethiolester6700 Ludwigshafen, April 3, 1969 l-Aza-cycloalkene- (2,3) -l-carboxylic acid thiol ester
Die vorliegende Erfindung betrifft neue wertvolle 1-Aza-cyeloalken-(2,3)-l-carbonsäurethiolester und Herbizide, die diese Wirkstoffe enthalten.The present invention relates to new valuable 1-aza-cyeloalken- (2,3) -l-carboxylic acid thiol ester and herbicides containing these active ingredients.
Es ist bekannt, S-Äthyl-hexahydro-1-H-azepin-l-carbothiolat zur selektiven Unkrautbekämpfung zu verwenden (US 3 198 786). Die herbizide Wirkung dieser Substanz befriedigt jedoch nicht.It is known to use S-ethyl hexahydro-1-H-azepine-l-carbothiolate to use selective weed control (US 3 198 786). the However, the herbicidal action of this substance is unsatisfactory.
Es wurde gefunden, daß l-Aza-cycloalken-(2,3)-l-carbonsäurethiolester der FormelIt has been found that l-aza-cycloalkene- (2,3) -l-carboxylic acid thiol ester the formula
CO-S-R,CO-S-R,
in der X Wasserstoff oder Halogen (Chlor, Brom) oder eine Alkoxygruppe (Methoxy, Äthoxy, Propoxy, Isopropoxy), η eine der ganzen Zahlen von 1 bis 8 und R einen gegebenenfalls durch Chlor substituierten aliphatischen Rest mit 1 bis 4 Kohlenstoffatomen (Methyl-, Äthyl-, Propyl-, Isopropyl-, n-1-Butyl-, n-2-Butyl-, Isobutyl-, tert.-Butyl-, 2-Chlorallyl-, 2,3-Dichlorallyl- oder 2,3,3-Trichlorallyl-) bedeutet, sehr gute herbizide Eigenschaften haben.in which X is hydrogen or halogen (chlorine, bromine) or an alkoxy group (Methoxy, ethoxy, propoxy, isopropoxy), η one of the integers from 1 to 8 and R one optionally substituted by chlorine aliphatic radical with 1 to 4 carbon atoms (methyl, ethyl, propyl, isopropyl, n-1-butyl, n-2-butyl, isobutyl, tert-butyl, 2-chloroallyl, 2,3-dichloroallyl or 2,3,3-trichloroallyl) means having very good herbicidal properties.
Die Wirkstoffe können beispielsweise durch Umsetzung der entsprechenden l-Aza-cycloalken-(2,3)-l-carbonsäurechloride mit einem aliphatischen Mercaptan in Anwesenheit eines säurebindenden Mittels, z.B. Triäthylamin, Pyridin oder Dimethylanilin, hergestellt werden. In manchen Fällen hat es sich als günstiger erwiesen, die entsprechenden Carbonsäurechloride mit einem Natrium- oder Kaliumsalz eines aliphatischen Mercaptans umzusetzen. Die unsubstituierten l-Aza-cycloalken-(2,3)-l-carbonsäurethiolester (X=H) lassen sich aus den entsprechenden 2-Halogen-l-aza-cycloalken-(2,3)-l-67/69 009841/1892 - 2 -The active ingredients can, for example, by implementing the appropriate l-aza-cycloalkene- (2,3) -l-carboxylic acid chlorides with an aliphatic mercaptan in the presence of an acid-binding agent, e.g. triethylamine, pyridine or dimethylaniline. In some cases it has been found to be more beneficial to implement corresponding carboxylic acid chlorides with a sodium or potassium salt of an aliphatic mercaptan. The unsubstituted Let l-aza-cycloalkene- (2,3) -l-carboxylic acid thiol ester (X = H) from the corresponding 2-halo-l-aza-cycloalkene- (2,3) -l-67/69 009841/1892 - 2 -
-2-- O.Z. 26 123 ■-2-- O.Z. 26 123 ■
carbonsäurethiolestern durch katalytische, hydrierende Dehalogenierung mit beispielsweise Raney-Nickel in einem geeigneten Lösungsmittel gewinnen.carboxylic acid thiol esters by catalytic, hydrogenating dehalogenation with, for example, Raney nickel in a suitable solvent to win.
Die folgenden Versuchsangaben erläutern die Herstellung der neuen l-Aza-cycloalkencarbonsäurethiolester. Die genannten Teile sind Gewichtsteile.The following experimental data explain the preparation of the new l-aza-cycloalkenecarboxylic acid thiol ester. The parts mentioned are Parts by weight.
2-Chlor-l-aza-cyclohepten-(2,3)-l-carbonsäure-n-l-butylthiolester Zu einer Lösung von 97 Teilen 2-Chlor-l-aza-cyclohepten-(2,3)-lcarbonsäurechlorid (belgische Patentschriften 582 478 und 61»9 063) in 500 Teilen Xylol gibt man bei 60 bis 700C unter Rühren aus zwei Vorratsbehältern gleichzeitig portionsweise ^5 Teile n-Butylmercaptan und 60 Teile Triäthylamin. Man erhitzt das Reaktionsgemisch anschließend noch 4 Stunden auf 100 bis HO0C filtriert von den abgeschiedenen Kristallen des Triäthylaminhydrochlorids ab und arbeitet das Filtrat destillativ auf. Es werden 115 Teile 2-Chlor-l-aza-cycloheptan-(2,3)-l-carbonsäure-n-1-butylthiolester vom Sdp.Q _ 131J bis 1350C erhalten. 2-chloro-1-aza-cycloheptene- (2,3) -l-carboxylic acid nl-butylthiol ester To a solution of 97 parts of 2-chloro-1-aza-cycloheptene- (2,3) -lcarboxylic acid chloride (Belgian patents 582 478 and 61 »9063) in 500 parts of xylene are added at 60 to 70 0 C, with stirring, of two storage tanks at the same time portionwise ^ 5 parts of n-butyl mercaptan and 60 parts of triethylamine. The reaction mixture is then heated to 100 to HO 0 C for a further 4 hours, the separated crystals of triethylamine hydrochloride are filtered off and the filtrate is worked up by distillation. There are obtained 115 parts of 2-chloro-l-aza-cycloheptane (2.3) -l-carboxylic acid n-1-butylthiolester, bp. Q _ 13 1 J to 135 0 C.
2-Chlor-l-aza-cyclotridecen-(2,3)-1-carbonsäure-sek.-butyl-thiolester2-chloro-1-aza-cyclotridecene (2,3) -1-carboxylic acid sec-butyl thiol ester
18 Teile sek.-Butylmercaptan werden durch Behandeln mit der stöchiometrischen Menge Natriummethylat wie üblich in das entsprechende Natriumsalz übergeführt. Man löst dieses Natriumsalz in 100 Teilen Dimethylformamid und gibt portionsweise unter. Rühren bei 70 bis 8O0C 56 Teile 2-Chlor-l-aza-cyclotridecen-(2,3)-lcarbonsäurechlorid zu. Das Reaktionsgemisch wird anschließend noch 5 Stunden bei 70 bis 800C gehalten und durch Filtration vom ausgefallenen Natriumchlorid befreit. Durch Destillation erhält man 30 Teile 2-Chlor-l-aza-cyclotridecen-(2,3)-l-carbonsäuresek.-butyl-thiolester vom Sdp.Q 5 179 bis 18Q0C. '18 parts of sec-butyl mercaptan are converted into the corresponding sodium salt as usual by treatment with the stoichiometric amount of sodium methylate. This sodium salt is dissolved in 100 parts of dimethylformamide and added in portions. Stirring at 70 to 8O 0 C, 56 parts of 2-chloro-l-aza-cyclotridecen- (2,3) to -lcarbonsäurechlorid. The reaction mixture is then kept at 70 to 80 ° C. for a further 5 hours and freed from the sodium chloride which has precipitated out by filtration. Distillation gives 30 parts of 2-chloro-1-aza-cyclotridecene (2,3) -l-carboxylic acid sec-butyl thiol ester with a bp. Q 5 179 to 18Q 0 C. '
l-Aza-cyclohepten-(2,3)-1-carbonsäure-äthylthiolester 80 Teile 2-Chlor-l-aza-cyclohefpten-(2J3)-l-carbonsäure-äthylthiolester werden in 500 Teilen Äthanol bei einem Druck von 10 Atmosphären und bei einer Temperatur von 40°C in Gegenwart von 20 Teilen Raney-Nickel als Hydrierkatalysator so lange hydriert bis keine Wasserstoffaufnahme mehr zu verzeichnen ist. Man fil- l-aza-cyclohepten (2,3) -1-carboxylic acid äthylthiolester 80 parts of 2-chloro-l-aza-cyclohe f PTEN (2 J 3) -l-carboxylic acid äthylthiolester in 500 parts of ethanol at a pressure of 10 atmospheres and at a temperature of 40 ° C. in the presence of 20 parts of Raney nickel as hydrogenation catalyst until hydrogen uptake is no longer recorded. Man fil-
0 0 9 8 k1/18 9 2 " 3 ~0 0 9 8 k 1/18 9 2 " 3 ~
- 3 - OiZ. 26 123- 3 - OiZ. 26 123
triert von festen Bestandteilen ab und engt das Filtrat ein.separates from solid components and concentrates the filtrate.
Der Rückstand wird in Chloroform aufgenommen und mit Wasser ausgeschüttelt. Aus der organischen Phase erhält man durch Destillation 36 Teile l-Aza-cyclohepten-(2,3)-l-carbonsäure-äthylthiolester vom Sdp.n ■, 96 bis 980C.The residue is taken up in chloroform and extracted with water. To 36 parts of l-aza-cyclohepten (2,3) -l-carboxylic acid äthylthiolester n ■ obtained from the organic phase by distillation, bp., 96 to 98 0 C.
Z-Methoxy-l-aza-cyclohepten-(2,3)-l-carbonsäureäthylthiolester 81I Teile Natriumäthylsulfid werden in 150 Teilen Dimethylformamid gelöst und unter Rühren bei 70 bis 800C mit 190 Teilen 2-Methoxyl-aza-cyclohepten-(2,3)-l-carbonsäurechlorid (erhältlich aus dem entsprechenden Lactimmethyläther mit Phosgen) portionsweise versetzt. Man rührt das Reaktionsgemisch anschließend noch 2 Stunden bei der gleichen Temperatur und befreit es dann durch Filtration von ausgeschiedenem Natriumchlorid. Durch Destillation erhält man aus dem Filtrat 173 Teile 2-Methoxy-l-asa-cyclohepten-(2,3)-lcarbonsäure-äthylthiolester vom Sdp.Q _ H2J0C Z-methoxyl-aza-cyclohepten (2,3) -l-carbonsäureäthylthiolester 8 1 I parts Natriumäthylsulfid are dissolved in 150 parts of dimethylformamide and under stirring at 70 to 80 0 C with 190 parts of 2-methoxyl-aza-cyclohepten- (2,3) -l-carboxylic acid chloride (obtainable from the corresponding lactime methyl ether with phosgene) is added in portions. The reaction mixture is then stirred for a further 2 hours at the same temperature and then freed from the sodium chloride which has separated out by filtration. Are obtained by distillation from the filtrate, 173 parts of 2-methoxy-l-asa-cyclohepten (2,3) -lcarbonsäure-äthylthiolester, bp. _ Q H 2 0 J C
Die übrigen Verbindungen können nach entsprechenden Verfahren hergestellt werden.The other compounds can be prepared by appropriate processes will.
Folgende Wirkstoffe seien beispielsweise, genannt:The following active ingredients are mentioned, for example:
l-Aza-cyclohepten-(2,3)-l-carbonsäure-n-propylthiolesterl-Aza-cycloheptene- (2,3) -l-carboxylic acid n-propylthiol ester
Sdp.n ι. 110 bis H2J C 2-Chlor-l-asa-cyclohepten-(2,3)-l-carbonsäure-äthylthiolesterSdp. N ι. 110 to H 2 JC 2-chloro-1-asa-cycloheptene- (2,3) -l-carboxylic acid ethylthiol ester
Sdp.n u 113 bis 1150C 2-Chlor-l-aza-cyclohepten-(2,3)-l-carbonsäure-propylthiolesterSdp. N u 113 to 115 0 C 2-chloro-l-aza-cyclohepten (2,3) -l-carboxylic acid propylthiolester
Sdp.Q ^ 115 bis 1200C 2-Chlor-l-aza-cyclohepten-(2,3)-l-carbonsäure-sek.-butylthiolesterSdp.Q ^ 115 to 120 0 C 2-chloro-l-aza-cyclohepten (2,3) -l-carboxylic acid sec-butylthiolester
Sdp.Q , 110 bis 1120C 2-Chlor-l-aza-cyclohepten-(2,3)-l-carbonsäure-tert.-butylthiolesterSdp.Q, 110 to 112 0 C 2-chloro-l-aza-cyclohepten (2,3) -l-carboxylic acid tert-butylthiolester
Sdp.n Ac 86 bis 880C , . 0,05Bp. N Ac 86 to 88 0 C,. 0.05
2-Chlor-l-aza-cyclononen-(2,3)-l-carbonsäure-nethylthiolester2-chloro-1-aza-cyclononen- (2,3) -l-carboxylic acid ethylthiol ester
Sdp.Q J4 1170C 2-Chlor-l-a.sa-cyclononen-(2,3)-l-carbonsäure-isopropylthiolesterBoiling point QJ 4 117 0 C 2-chloro-la.sa-cyclononen- (2,3) -l-carboxylic acid isopropylthiol ester
Sdp.Q , 115 bis 1170CSdp.Q, 115 to 117 0 C
2-Chlor-l-asa~cyclononen-(2,3)-l-carbonsäure-isobutylthiolester2-chloro-l-asa ~ cyclononen- (2,3) -l-carboxylic acid isobutylthiol ester
Sdp.Q nc; 122 bisSdp.Q nc; 122 to
009841/1892009841/1892
-H- O. Z. 2.6 123'-H- O. Z. 2.6 123 '
2-Chlor-l-aza-cyclononen-(2,3)-1-carbonsäure-tert.-butylthiolester2-chloro-1-aza-cyclononen- (2,3) -1-carboxylic acid tert-butylthiol ester
Sdp.Q 2 122 bis 1250CSdp.Q 2 122 to 125 0 C
2-Chlor-l-aza-cyclotrideeen-(2,3)-l-carbonsäure-äthylthiolester.Ethyl thiol ester of 2-chloro-l-aza-cyclotrideene- (2,3) -l-carboxylic acid.
Q 3 159 bis l6l°CQ 3 159 to 16 ° C
3 2-Chlor-l-aza-cyclotridecen-(2,3)-l-carbonsäure-isopropylthiolester 3 2-Chloro-1-aza-cyclotridecene (2,3) -l-carboxylic acid isopropylthiol ester
Sdp.Q 2 1**9 bis 151°CBp Q 2 1 ** 9 to 151 ° C
2-Chlor-l-aza-cyclotridecen-(2,3)-1-carbonsäure-sek.-butylthiolester Sdp.Q 5 1800C 2-Chlor-l-aza-cyclotridecen-(2,3)-l-carbonsäure-n-butylthiolester2-chloro-1-aza-cyclotridecene (2,3) -1-carboxylic acid sec-butylthiol ester, boiling point Q 5 180 0 C 2-chloro-1-aza-cyclotridecene (2,3) -l-carboxylic acid -n-butylthiol ester
Sdp.Q-2 166 bis 1690CSdp.Q- 2 166 to 169 0 C
2-Chlor-l-aza-cyclotridecen-(2,3)-1-carbonsäure-tert.-butylthiolester Sdp.Q 2 1630C. 2-Methoxy-l-aza-cyclononen-(2,3)-1-carbonsäureäthylthiolester2-chloro-l-aza-cyclotridecen- (2,3) -1-carboxylic acid tert-butylthiol ester Bp.Q 2 163 0 C. 2-methoxy-l-aza-cyclononen- (2,3) -1- ethylthiol carboxylate
Q 2 116°C 2-Methoxy-l-aza-cyclononen-(2 ,3)-l-carbonsäure-äthylthiolesterQ 2 116 ° C 2-methoxy-1-aza-cyclononen- (2, 3) -l-carboxylic acid ethylthiol ester
Sdp.Q , 135 bis 14O°C 2-Methoxy-l-aza-cyclotridecen-(2,3)-l-carbonsäure-äthylthiolesterBp Q, 135 to 140 ° C Ethyl thiol ester of 2-methoxy-l-aza-cyclotridecene (2,3) -l-carboxylic acid
Sdp.Q 75 150°CBp Q 75 150 ° C
2-Methoxy-l-aza-cyclotridecen-(2,3)-1-carbonsäure-sek.-butylthiolester ' Sdp.Q 4 156°C2-Methoxy-1-aza-cyclotridecene (2,3) -1-carboxylic acid sec-butylthiol ester, bp Q 4 156 ° C
Die Wirkstoffe können als Lösungen, Emulsionen, Suspensionen oder Stäubemittel angewandt werden. Die Anwendungsformen richten sich ganz nach den Verwendungszwecken; sie sollen in jedem Fall eine feine Verteilung gewährleisten.The active ingredients can be used as solutions, emulsions, suspensions or dusts. The forms of application are directed according to the intended use; they should ensure a fine distribution in any case.
Zur Herstellung von direkt versprühbaren Lösungen können Kohlenwasserstoffe, wie Tetrahydronaphthalin, und alkylierte Naphthaline als Spritzflüssigkeit verwendet werden.Hydrocarbons, such as tetrahydronaphthalene, and alkylated naphthalenes can be used as spray liquids.
Wäßrige Anwendungsformen können aus Emulsionskonzentraten, Pasten oder netzbaren Pulvern (Spritzpulver) durch Zusatz von Wasser bereitet werden. Zur Herstellung von Emulsionen können die Substanzen als solche oder in einem Lösungsmittel gelöst mittels Netzoder Dispergiermitteln in Wasser oder organischen Lösungsmitteln homogenisiert werden. Es können aber auch aus wirksamer Substanz Emulgier- oder Dispergiermittel und eventuell Lösungsmittel bestehende Konzentrate hergestellt werden, die zur Verdünnung Aqueous application forms can be obtained from emulsion concentrates, pastes or wettable powders (wettable powders) can be prepared by adding water. The substances can be used to produce emulsions as such or dissolved in a solvent by means of wetting agents or dispersants in water or organic solvents be homogenized. However, it is also possible to prepare concentrates consisting of active substances, emulsifiers or dispersants and possibly solvents, which are used for dilution
009841/1892 '009841/1892 '
- 5 - O.Z. 26 123- 5 - O.Z. 26 123
mit Wasser geeignet sind.with water are suitable.
Stäubemittel können durch Mischen oder gemeinsames Vermählen der wirksamen Substanzen mit einem festen Trägerstoff hergestellt werden.Dusts can be produced by mixing or grinding the active substances can be produced with a solid carrier.
Die folgenden Beispiele erläutern die Anwendung der Wirkstoffe.The following examples explain the use of the active ingredients.
Sandboden wurde in Versuchsgefäße gefüllt, mit Samen von Brassica sp. (Kohlarten), Oryza sativa (Reis), Digitaria sanguinalis (Bluthirse), Setaria viridis (grüne Borstenhirse), Echinochloa crus galli (Hühnerhirse), Avena fatua (Plughafer), Alopecurus myosuroides (Ackerfuchsschwanz) und Lolium perenne (deutsches Weidelgras) besät und unmittelbar danach mit den Wirkstoffen 2-Chlor-l-aza-' cyclononen-(2,3)-l-carbonsäure-thiol-tert.-butylester I und im Vergleich dazu mit S-'Athyl-hexahydro-l-H-azepin-l-carbothiolat (II) jeweils in einer Aufwandmenge, entsprechend 3 kg Wirkstoff je ha, dispergiert in 500 Liter Wasser je ha," behandelt.Sandy soil was filled into test vessels with seeds of Brassica sp. (Cabbage species), Oryza sativa (rice), Digitaria sanguinalis (blood millet), Setaria viridis (green millet), Echinochloa crus galli (chicken millet), Avena fatua (plughoat), Alopecurus myosuroides (Black foxtail) and Lolium perenne (German ryegrass) sown and immediately afterwards with the active ingredients 2-chloro-l-aza- ' cyclononen- (2,3) -l-carboxylic acid thiol tert-butyl ester I and in comparison with S-'ethyl-hexahydro-l-H-azepine-l-carbothiolate (II) in each case in an application rate corresponding to 3 kg of active ingredient per ha, dispersed in 500 liters of water per hectare, "treated.
Die Versuchsergebnisse nach 5 Wochen sind aus nachfolgender Tabelle zu ersehen:The test results after 5 weeks are from the table below to see:
Brassioa sp,Brassioa sp,
Oryza sativaOryza sativa
Digitaria sanguinali3 Echinochloa crus galli Avena fatuaDigitaria sanguinali3 Echinochloa crus galli Avena fatua
Alopecurus myosuroidesAlopecurus myosuroides
Lolium perenne 70 50-60Lolium perenne 70 50-60
0 = keine Schädigung IQO 5 totale Schädigung,0 = no damage IQO 5 total damage,
- 6 0Q3841/1892 - 6 0Q3841 / 1892
- 6 - O.Z. 26 123- 6 - O.Z. 26 123
Im Gewächshaus wurden die Pflanzen einj. Rispengras (Poa annua), Knäuelgras (Dactylis glomerata), Plughafer (Avena fatua), Hühnerhirse (Echinochloa crus galli), Kohlarten (Brassica sp.) und Reis (Oryza sativa) bei einer Wuchshöhe von 2 bis 14 cm mit einer 3 kg/ha entsprechenden Menge 2-Chlor-l-aza-cyclononen-(2,3)-lcarbonsäure-thiol-tert.-butylester I, dispergiert in 500 Liter Wasser je ha, behandelt. Nach 3 bis 4 Wochen wurde festgestellt, daß die Ungräser (einj. Rispengras, Knäuelgras, Flughafer, Hühnerhirse) zum großen Teil abgestorben waren, während Kohl und Reis ohne Schaden weiterwuchsen.In the greenhouse, the plants were einj. Bluegrass (Poa annua), Ball grass (Dactylis glomerata), plughoats (Avena fatua), barnyard millet (Echinochloa crus galli), cabbage species (Brassica sp.) And Rice (Oryza sativa) at a height of 2 to 14 cm with a 3 kg / ha corresponding amount of 2-chloro-1-aza-cyclononen- (2,3) -lcarboxylic acid-thiol-tert-butyl ester I, dispersed in 500 liters of water per hectare. After 3 to 4 weeks it was found that the grass weeds (including bluegrass, ball grass, wild oats, barnyard millet) had largely died, while cabbage and rice continued to grow without damage.
Biologisch gleich wirksam mit I sind u.a.:Biologically equally effective with I are, among others:
l-Aza-cyclohepten-(2,3)-1-carbonsäure-äthy!thiolester 2-Chlor-l-aza-cyclohepten-(2,3)-1-carbonsäure-n-butylthiolester 2-Chlor-l-aza-cyclotridecen-(2,3)-1-carbonsäure-sek.-butylthiolester. 1-Aza-cycloheptene- (2,3) -1-carboxylic acid ethy! thiol ester 2-chloro-1-aza-cycloheptene- (2,3) -1-carboxylic acid n-butylthiol ester 2-chloro-1-aza-cyclotridecene (2,3) -1-carboxylic acid sec-butylthiol ester.
" - 7 -009841/1892"- 7 -009841/1892
Claims (2)
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19691917534 DE1917534A1 (en) | 1969-04-05 | 1969-04-05 | 1-Aza-cycloalkene- (2,3) -1-carboxylic acid ethiol ester |
| ZA702102A ZA702102B (en) | 1969-04-05 | 1970-03-26 | 1-azacycloalkene-(2,3)-1-carboxylic acid thiol esters |
| AU13204/70A AU1320470A (en) | 1969-04-05 | 1970-03-31 | 1-azacycloalkene - (2,3)-carboxylic acid thiol esters |
| FR7011938A FR2038278A1 (en) | 1969-04-05 | 1970-04-02 | 1-aza-2,3-cycloalkene-1-thiocarboxylic acid - acid s-esters |
| NL7004732A NL7004732A (en) | 1969-04-05 | 1970-04-02 | |
| BE748456D BE748456A (en) | 1969-04-05 | 1970-04-03 | S- 1-AZA-2,3-CYCLOALCENE-1- L-AZA-2,3-CYCLOALCENE-1- THIOCARBOXYL ESTERS |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19691917534 DE1917534A1 (en) | 1969-04-05 | 1969-04-05 | 1-Aza-cycloalkene- (2,3) -1-carboxylic acid ethiol ester |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1917534A1 true DE1917534A1 (en) | 1970-10-08 |
Family
ID=5730411
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE19691917534 Pending DE1917534A1 (en) | 1969-04-05 | 1969-04-05 | 1-Aza-cycloalkene- (2,3) -1-carboxylic acid ethiol ester |
Country Status (6)
| Country | Link |
|---|---|
| AU (1) | AU1320470A (en) |
| BE (1) | BE748456A (en) |
| DE (1) | DE1917534A1 (en) |
| FR (1) | FR2038278A1 (en) |
| NL (1) | NL7004732A (en) |
| ZA (1) | ZA702102B (en) |
-
1969
- 1969-04-05 DE DE19691917534 patent/DE1917534A1/en active Pending
-
1970
- 1970-03-26 ZA ZA702102A patent/ZA702102B/en unknown
- 1970-03-31 AU AU13204/70A patent/AU1320470A/en not_active Expired
- 1970-04-02 FR FR7011938A patent/FR2038278A1/en not_active Withdrawn
- 1970-04-02 NL NL7004732A patent/NL7004732A/xx unknown
- 1970-04-03 BE BE748456D patent/BE748456A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| NL7004732A (en) | 1970-10-07 |
| BE748456A (en) | 1970-10-05 |
| ZA702102B (en) | 1971-01-27 |
| AU1320470A (en) | 1971-10-07 |
| FR2038278A1 (en) | 1971-01-08 |
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