IE45759B1 - Isomeric mixture of trimethylperhydroazepine -1- thiocarboxylic acid s-ethyl esters, process for the manufacture of this mixture and also its use as a herbicide - Google Patents
Isomeric mixture of trimethylperhydroazepine -1- thiocarboxylic acid s-ethyl esters, process for the manufacture of this mixture and also its use as a herbicideInfo
- Publication number
- IE45759B1 IE45759B1 IE1457/77A IE145777A IE45759B1 IE 45759 B1 IE45759 B1 IE 45759B1 IE 1457/77 A IE1457/77 A IE 1457/77A IE 145777 A IE145777 A IE 145777A IE 45759 B1 IE45759 B1 IE 45759B1
- Authority
- IE
- Ireland
- Prior art keywords
- isomeric mixture
- substituted
- preparation
- formula
- acid
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/16—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms
- C07D295/18—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms by radicals derived from carboxylic acids, or sulfur or nitrogen analogues thereof
- C07D295/182—Radicals derived from carboxylic acids
- C07D295/185—Radicals derived from carboxylic acids from aliphatic carboxylic acids
Abstract
A herbicide comprises S-ethyl 3,3,5- and/or 3,5,5-trimethylperhydroazepine-1-thiocarboxylate(s) of the formula(e) and/or as at least one active substance. A process for the production of the herbicide is described.
Description
The present invention is concerned with a new 1:1-isomeric mixture of trimethylperhydroazepine-l-thiocarboxylic acid
S-ethyl esters, a process for the manufacture of such a mixture and also its use as a herbicide.
The problem upon which the present invention is based has been to provide a herbicidally active agent having a wide spectrum of selectivity towards crop plants and a very good herbicidal action against weeds.
This problem is solved in accordance with the present 10 invention by the isomeric mixture defined in the following paragraph.
The present invention accordingly provides a 1:l-isomeric mixture of 3,3,5-trimethylperhydro-azepine-l-thiocarboxylic acid S-ethyl ester of the formula Ia
-245759 and 3,5,5-trimethyl-perhydro-azepine-l-thiocarboxylic acid
S-ethyl ester of the formula lb
CO-S-C2H5 (lb)
CH
German Offenlegungsschrift No. 2,333,397 describes and claims 5 compounds of the general formula
where X denotes oxygen or sulphur, R1 denotes ethyl or 2 or radicals which are independently selected from ethyl and 2 methyl, and R denotes a hydrocarbon radical which is unsubstituted or substituted by one or more substituents independently selected from halogen, hydroxyl, cyano, alkoxy
-3and nitro, nitro if present being attached to a benzene ring, and their use as herbicides.
The isomeric mixture of ethyl esters of the present invention has the special advantage that it has an outstanding herbicidal action, for example against the weeds Triticum, Hordeum and Setaria. This outstanding herbicidal action against Triticum, Hordeum and Setaria is completely unexpected, because the corresponding isomeric mixture of methyl esters and the corresponding isomeric mixture of n-propyl esters both of which are disclosed in German Offenlegungsschrift No. 2,333,397 (and which are of course structurally analogous) do not have a satisfactory herbicidal action against all these weeds. As can be seen from the test results given in Example 3 below the corresponding isomeric mixture of npropyl esters is ineffective against Triticum and Hordeum and both the corresponding isomeric mixture of n-propyl esters and the corresponding isomeric mixture of methyl esters have a minimal effectiveness against Setaria.
The isomeric mixture of the present invention is also distinguished by an outstanding herbicidal action against other monocotyledonous weeds, for example, Avena, Alopecurus Echinochloa, Digitaria, Sorghum and Poa.
-448739
Owing to its excellent selective properties, the isomeric mixture of the present invention can be used in agricultural crops, for example cauliflower, sugar beet, seeded tomato, cotton and soya crops.
The isomeric mixture of the present invention can also be used in maize and sorghum, it being of advantage to mix antidotes, for example 8-naphthalic anhydride or N,Ndiallyldichloracetamide, with the seed grain or spraying preparation respectively.
A further advantage of the isomeric mixture of the present invention is that it also has growth-regulating properties.
The isomeric mixture acts satisfactorily even at rates of application of from 1kg of active substance per hectare, and, owing to its surprisingly wide spectrum of selectively, can be used in quantities of up to 8 kg of active substance per hectare before sowing by incorporation in the soil.
The present invention accordingly also provides a herbicidal preparation which comprises the isomeric mixture of the present invention in admixture or conjunction with a suitable carrier.
-5§3 1 « The present invention further provides a method of protecting a living plant against weeds, wherein the area in the. vicinity of the living plant is treated with the isomeric mixture of the present invention.
The present invention further provides a method of protecting a crop area against weeds, wherein the crop area is treated with the isomeric mixture of the present invention.
The present invention further provides a pack which comprises the isomeric mixture of the present invention together with instructions for its use as a herbicide.
The isomeric mixture of the present invention can be used either alone or in admixture with other active substances.
Depending on the purpose desired, there are mentioned in this connection by way of example the following herbicidally active substances, which, if desired, may be added immediately before the use of the isomeric mixture of the present invention:
substituted anilines, substituted aryloxycarboxylic acids and also salts, esters and amides thereof, substituted ethers,
-645789 substituted arsonic acids and also salts, esters, and amides thereof,
substi tuted benzimidazoles, substi tuted benzisothiazoles, substituted benzthiadiazinone dioxides, substituted benzoxazines, substituted benzoxazi nones, substituted benzthiazoles, substituted benzthiadiazines, substi tuted biurets, substituted quinolines, substi tuted carbamates, substi tuted aliphatic carboxylic acids and also salts,
esters and amides thereof, substituted aromatic carboxylic acids and also salts, esters and amides thereof,
substi tuted carbamoylalkyl-thio- or dithio-phosphates, substituted qui nazoli nes, substi tuted cycloalkylamidocarbothiolic acids and also salts,
esters and amides thereof, substituted cycloalkylcarbonamido-thiazoles , substituted dicarboxylic acids and also salts, esters and amides thereof,
substituted dihydrobenzofuranylsulphonates , substituted disulphides, substi tuted di pyridylium salts,
-7substituted dithiocarbamates, substituted dithiophosphoric acids and also salts, esters and amides thereof, substituted ureas, substituted hexahydro-lH-carbothioates,
substituted hydantoins, substituted hydrazides, substituted hydrazonium salts, substituted isoxazolepyrimidones, 10 substituted imidazoles, substi tuted isothiazolepyrimidones, substituted ketones, substituted naphthoquinones, substi tuted aliphatic nitriles, 15 substituted aromatic nitriles, substituted oxadiazoles, substituted oxadiazinones, substi tuted oxadi azolidinediones, substi tuted oxadiazinediones, 20 substituted phenols and also salts and esters, thereof, substituted phosphonic acids and also salts, esters and
amides thereof, substituted phosphonium chlorides, substituted phosphonalkylglycines, substituted phosphites,
-845759 substituted phosphoric acids and salts, esters and amides thereof, substituted piperidines, substituted pyrazoles, substituted pyrazolalkylcarboxylic acids and also salts, esters and amides thereof, substituted pyrazolium salts,
substi tuted pyrazolium alkyl sulphates, substi tuted pyri dazi nes, substituted pyridazones, substi tuted pyridine carboxylic acids and also salts, esters
and amides thereof,
substi tuted pyridines, substi tuted pyridine carboxylates, substi tuted pyri di nones, substi tuted pyrimidones, substituted pyrrolidine carboxylic acids and also salts,
esters and amides thereof, substituted pyrrolidines, substituted aryl sulphonic acids and also salts, esters and amides thereof, substituted styrenes, substituted tetrahydro-oxadiazinediones, substituted tetrahydromethanoindenes, substituted tetrahydro-diazole-thiones ,
-945759 substituted tetrahydro-thiadiazine-thiones, substituted tetrahydro-thiazolediones, substituted thiadiazoles, substituted aromatic thiocarboxylic acid amides, substituted thiocarboxylic acids and also salts, esters and amides thereof, substituted thiolcarbamates, substituted thiophosphoric acids and also salts, esters and amides thereof, substituted triazines, substituted triazoles, substituted uracils and substituted uretidinediones.
There may also be used other additives, for example nonphytotoxic additives, which produce with herbicides a synergistic increase in action, for example, wetting agents, emulsifiers, solvents and oily additives.
The isomeric mixture of ethyl esters of the present invention is advantageously used in .the form of herbicidal preparations, for example powders, strewable preparations, granules, solutions, emulsions or suspensions, with the addition of liquid and/or solid vehicles or diluents and, if desired, of surface-active agents, for example wetting, adherent
-1045759 emulsifying and/or dispersing agents.
Suitable liquid carriers are, for example, water, aliphatic hydrocarbons, aromatic hydrocarbons, for example, benzene, toluene and xylene, cyclohexanone, isophorone, dimethyl sulphoxide and dimethylformamide, and also mineral oil fracti ons.
As solid carriers there are suitable, for example, mineral earths, for example tonsil, silica gel, talcum, Kaolin, attaclay, limestone and silicic acid, and vegetable products, for example, meals.
As surface-active agents there may be mentioned, for example, calcium lignin sulphonate, polyoxyethylalkyl-phenyl ethers, naphthalene sulphonic acids and salts thereof, phenol sulphonic acids and salts thereof, formaldehyde condensates, fatty alcohol sulphates and also substituted benzene sulphonic acids and salts thereof.
The proporation of active substance in the various herbicidal preparations may vary within wide limits. For example, the preparations may contain 10 to 80% by weight of active compound(s), 90 to 20% by weight of liquid or solid carrier and, if desired, also up to 20% by weight of surface-active agent(s).
The active isomeric mixture of the present invention may be applied in the usual manner, for example, with water as carrier in quantities of spray liquor of 100 to 1000 litres per hectare. It is also possible to apply the active mixture by the so-called “low volume and ultra-low volume methods, and also in the form of so-called microgranules.
The present invention further provides a process for the manufacture of the isomeric mixture of the ester of the formula- Ia and the ester of the formula lb, wherein an isomeric mixture (if desired dissolved in a solvent) of trimethyl-
(a) is reacted, if desired in the presence of an acid-binding
-1245759 agent, with chloro-thioformic acid S-ethyl ester of the formula
Cl-C0-S-C2H5, or (b) is reacted in the presence of a base with carbon 5 oxysulphide of the formula
O=C=S to form salts of such a base of the general formulae
-1345759 in which B represents a cation derived from the base, and the salts are treated with an ethylating agent of the general formula
H5c2-z, in which Z represents a halogen atom, an ethyl sulphuric acid group or a toluene sulphonic acid group, or (c) is reacted with phosgene of the formula ci
Cl to form trimethylperhydroazepine-l-carboxylic acid chlorides 10 of the formulae
-14457S9 which are then reacted with ethyl mercaptan of the formula
HgCg-SH or with a salt of such a mercaptan, if desired in the presence 5 of an acid-binding agent.
The product of the process may be isolated in a known manner.
As bases or acid-binding agents there may be used all the usual proton acceptors. For this purpose there are suitable organic bases, for example tertiary amines, for example triethylamine or Ν,Ν-dimethylaniline, or pyridine bases, and suitable inorganic bases, for example oxides, hydroxides and carbonates of alkali and alkaline earth metals. Liquid bases may serve simultaneously as solvents. This applies also to the liquid starting bases, if they are used in excess as acid capturer.
-1545758
The reaction of the components may be carried out at between 0 and 120°C, but generally at room temperature.
For the synthesis of the isomeric mixture of the present invention the reactants are preferably used in equimolar quantities.
Suitable reaction media are solvents inert towards the reactants, either alone or in admixture with water.
Amongst many such reaction media the following may be mentioned by way of example, namely aliphatic and aromatic hydrocarbons, for example petroleum ether, cyclohexane, benzene, toluene and xylene, halogenated hydrocarbons, for example methylene chloride, chloroform, carbon tetrachloride and halogenated ethylenes, ether-like compounds, for example diethyl ether, diisopropyl ether, tetrahydrofuran and dioxan, ketones, for example acetone, methyl isobutyl ketone and isophorone, esters, for example methyl and ethyl acetates, acid amides, for example dimethylformamide and hexamethylphosphoric acid triamide, and carboxylic acid nitriles, for example acetonitrile.
Finally, the isolation of the isomeric mixture of the present invention may be carried out in a manner known per se by
-1645759 distilling off the solvents used under atmospheric or reduced pressure, optionally after treatment with acid or basic agents to remove undesired by-products.
The starting compounds for preparing the isomeric mixture of the present invention are known or can be prepared by methods known per se. The isomeric mixture of the present invention containing the two isomers 3,3,5-trimethylperhydro-azepine-l-thiocarboxylic acid S-ethyl ester and 3,5,5-trimethyl-perhydro-azepine-1-thiocarboxylic acid Sethyl ester in the ratio by weight of 1:1 is a pale yellow coloured oil having a feebly aromatic odour, which is insoluble in water, but readily dissolves in all organic solvents, for example hydrocarbons, halogenated hydrocarbons, ethers, ketones, carboxylic acid esters, carboxylic acid amides, carboxylic acid nitriles, alcohols, carboxylic acids, sulphoxides and many others.
The following Examples illustrate the invention. Example 1 illustrates the process of the present invention and Examples 2 and 3 illustrate the possibilities of use of the isomeric mixture of the present invention.
Example 1
66.4 ml of a l:l-isomeric mixture of 3,3,5-trimethyl- and
-17457 59
3,5,5-trimethyl-perhydro-azepine were dissolved in 150 ml of diisopropyl ether, and 25 gms of chloro-thioformic acid
S-ethyl ester were added dropwise at room temperature while stirring. The reaction mixture was stirred for a further hour, then extracted by agitation with water, then with dilute hydrochloric acid and again with water, the ether phase was dried over magnesium sulphate, the solvent was distilled off in vacuo and finally the remainder of the solvent was removed under a high vacuum.
45 gms (98% of the theoretical yield) of 3,3,5(3,5,5)trimethyl-perhydro-azepine-l-thiocarboxylic acid S-ethyl 20 ester having an n^ value of 1.5041 were obtained. By the addition of a sodium hydroxide solution to the first aqueous extract 28.3 gms of the starting base used in excess were recovered.
Analysis: Calculated C 62.83% H 10.11% N 6.11%
Found C 62.66% H 10.28% N 5.97%
1
Example 2
In a series of tests carried out in a greenhouse the plants 20 listed in the Table below were treated before their emergence
-185759 with the agents mentioned at the rate of application of 3 kg of active substance per hectare. For this purpose the agents were in each case applied uniformly to the soil in the form of an aqueous dispersion at the rate of
500 litres per hectare, and then worked into the soil.
Three weeks after the treatment the results showed that the isomeric mixture of the present invention was better than the agent used for comparison. The results are expressed by a numerical scale extending from 0 to 10, the value 0 representing total destruction and the value 10 representing no damage.
-1945750
BOd uinq6-ios
ΒΜΒψ.ΐβ,ΐα
BIJB13S
Boiqoouiqog srunoadOLv
Euaay uinspuoH uinoLqioj.
ao LH
UEag bKos uoqqog oousqsqns OALqoB J.0 sq/6>|
P c
Φ >
c
P c
φ
ΙΛ
Φ
X.
CL ω
Δ
P
Μα φ
u c
<ϋ
P w
Δ =5
V)
Φ >
P o
c o
o'·' o
o o
o o
o
O ' o
o co o c p o
1 ·<—
co
O CO u Cnp c <0 1 o o xj •ι- O •r~ >,»r- Ό «r- -C -C U X- P P $- fO Ο·«- Φ O U Φ c CL O U Φ c o ι .,- <0 CL Φ ·Γ“ r— r— -—co r— P >>>» >» u JC X C P Δ 3 P o o c P i. -σ ω .a ω φ Φ P ω E i- •r- P ε r— <Λ cn •f- «J i~ ff} O QJ <0 i- υ CL X s- XJ ε P O CL »— Q) P ro 1 ·!- E W IO JZ c t— •σ Ο Φ CO 1 o (0 LDP i- ο p r- z o P P « 1 φ CO « Λ o o in t— p L. p <30 Ζ Φ T3 P c * t (/) ο v) cn I P QJ co ω ω P r— »— <0 P II II —' c Ό * >> ε in «ι-1— Ρ Φ CO Δ (O Φ o o * Q->> C P P x> t. t—· co Φ jc Φ ‘1- · UJ L. P « Ν P cn c o 1 <0 c CO rtJ φ CO z in o o
Example 3
Description of the tests
The purpose of the comparative tests carried out in this Example was to determine the herbicidal action of the isomeric mixture of the present invention as compared with the structurally analogous corresponding isomeric mixture of methyl esters and corresponding isomeric mixture of n-propyl esters disclosed in German Offenlegungsschrift No. 2,333,397.
In the comparative tests the cultivated plants and weeds listed in the Table of results below were treated under hot-house conditions prior to their emergence with the listed agents at a rate of application of approximately 3 kg of active substance per hectare. For this purpose the agents were in each case applied uniformly over the surface of the soil in the form of an aqueous dispersion using 500 liters per hectare, and then finally worked into the Soil.
Three weeks after the treatment an evaluation of the effectiveness of the agents was carried out by a visual control according to the following numerical scale:
-2145759
100% destruction 6 = 40% destruction 90% destruction 7 = 30% destructi on 80% destruction 8 = 20% destruction 70% destruction 9 = 10% destruction 60% destructi on 10 = no damage 50% destruction
-2245759
Test Results lunqBaos BLjet Lblq
ELUBqes eoLipouLipg uinepuoH uino^ui eoiy UB98 bAos 1103403 σ
co
CM
O O r— r“*
O α
•r*
P
Φ
JS
P
4O ω
-σ c
□
CL ε
o >>
-C
P ω
ε ί1 υ
in r— 1 0 1 O >> S- 5- LO X Ό O o TJ * Q >>♦1- >>‘r- co -Ω x: 0 P .c υ Ρ ·—· u s- <0 4- ί- (0 4— to ro Φ •f— φ •ι— ·* 0 ο. υ Ω. U ί- co 0 1 *r* .c 1 τ- JS *>·Γ“ j— r** 0 ι— Γ” Ο CO JZ .. >»>> tn >»>, <Ζ) P tn _C X tn j= X ιη 4- 1 -a 4- P 0 cn 4- Ρ Ο cn O r* i- c O Φ -Ω C O Φ η α I Φ 3 ε i- 3 ε □ Φ Φ P O Φ •P- <0 cn Φ •γ* <0 ί. σ» u c ω CL S- u 0 Φ L. ί- α Φ φ 3·ι- Φ ε 3 p 0 s- r— χ-». 3 ρ ο Ρ Ρ— > P CL o P 1 ·»“ O c r-χ P 1 ·γ“ tn e γ*. X O r- 0 X —-J= P Φ cn X .—._c: φ Φ cn •1- N >» •P“ in p w 4- co •r— ιη ρ Ρ co E ¢0 -C c ε r | φ 4- « ε * » r— Ρ Λ 1 1 * 0 in r» 0 co in >»ο CO U Ο Φ m o t. 1 p— co υ * 1 Ω. co •r· S- 1 •r* •r- CO Φ >J c co •r· CO Φ Ο c co ί- Ό tO t- i- *—<· c x: to * ί. *—· c ί- to * Φ >) (0 Φ tn *r- p E CM o m *r- α. Ε CM E JZ Ό CL ε CL φ ί- ε *· Q. ι ί- O t· *f“ ε o co φ ε ο . o co φ C ο . V) Φ O o (Λ « Ν 1 0 0 ω * Ν I 0 0 CL 0 MfO fl(/) 'x-'Z HH co <0 to
Untreated Control
-2345759
Evaluation
The test results clearly show the outstanding herbicidal action of the isomeric mixture of the present invention coupled with its selectivity with respect to the cultivated plants cotton and soya bean. This herbicidal action can be seen to be superior to the structurally analogous isomeric mixtures used for comparison. The isomeric mixtures used for comparison showed both an insufficient action against the weeds and an inadequate selectivity with respect to the cultivated plants.
Claims (19)
- I. A l:l-isomeric mixture of 3,3,5-trimethyl-perhydroazepine-l-thiocarboxylic acid S-ethyl ester of the formula Ia and 3,5,5-trimethyl-perhydro-azepine-l-thiocarboxylic acid S-ethyl ester of the formula Ib -2545759
- 2. A process for the manufacture of an isomeric mixture as claimed in claim 1, wherein a 1:1 isomeric mixture of trimethylperhydroazepines of the formulae 5 (a) is reacted with chloro-thioformic acid S-ethyl ester of the formula Cl-CO-S-CgHg, or (b) is reacted in the presence of a base with carbon oxysulphide of the formula 10 O=C=S to form salts of such a base of the general formulae -2645759 in which B represents a cation derived from the base, and the salts are treated with an ethylating agent of 5 the general formula h 5 c 2 -z, in which Z represents a halogen atom, an ethyl sulphuric acid group or a toluene sulphonic acid group, or -2745759 (c) is reacted with phosgene of the formula Ci Cl to form trimethylperhydroazepine-l-carboxylic acid chlorides of the formulae which are then reacted with ethyl mercaptan of the formula h 5 c 2 -sh or with a salt of such a mercaptan.
- 3. A process as claimed in claim 2 wherein each of the 10 reactions with the chloro-thioformic acid S-ethyl ester and with the ethyl mercaptan or salt thereof is carried -28out in the presence of an acid-binding agent.
- 4. A process as claimed in claim 2, conducted substantially as described herein.
- 5. A process as claimed in claim 2, conducted 5 substantially as described in Example 1 herein.
- 6. A herbicidal preparation which comprises as isomeric mixture as claimed in claim 1, in admixture or conjunction with a suitable carrier.
- 7. A preparation as claimed in claim 6, which is in the 10 form of a powder, a strewable preparation, granules, a solution, an emulsion or a suspension.
- 8. A preparation as claimed in claim 6 or 7, wherein the isomeric mixture is present in an amount of 10 to 80% by weight. 15
- 9. A preparation as claimed in any one of claims 6 to 8, containing a single surface-active in an amount of up to 20% by weight.
- 10. A preparation as claimed in any one of claims 6 to 8, containing two or more surface-active agents in a total -29amount of up to 20% by weight.
- 11. A herbicidal preparation as claimed in claim 6 and substantially as described in Example 2 herein.
- 12. A method of protecting a living plant against weeds, wherein the area in the vicinity of the living plant is treated with an isomeric mixture as claimed in claim 1.
- 13. A method as claimed in claim 12, wherein the area is treated with a herbicidal preparation as claimed in any one of claims 6 to 11. j c r
- 14. A method as claimed in claims 12 or 13, wherein the isomeric mixture.is used for the treatment in an amount within the range of from 1 to 8 kg per hectare.
- 15. A method as claimed in claim 12, conducted substantially as described ih Example 2 herein.
- 16. A method of protecting a crop area against weeds, wherein the crop area is treated with an isomeric mixture as claimed in claim 1.
- 17. A method as claimed in claim 16, wherein the crop area is treated with a herbicidal preparation as claimed in any one of claims 6 to 11. 4S7S9
- 18. A method as claimed in claim 16 or 17, wherein the isomeric mixture is used for the treatment in an amount within the range of from 1 to 8 kg per hectare.
- 19. A method as claimed in any one of claims 16 to 18, 5 wherein the crop is a cauliflower, sugar beet, seeded tomato, cotton,·soya , maize or sorghum crop.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19762632676 DE2632676A1 (en) | 1976-07-16 | 1976-07-16 | TRIMETHYLPERHYDROAZEPIN-1-THIOCARBONIC ACID S-AETHYL ESTER, METHOD FOR PRODUCING THESE COMPOUNDS AND THIS CONTAINING HERBICIDE AGENT |
Publications (2)
Publication Number | Publication Date |
---|---|
IE45759L IE45759L (en) | 1978-01-16 |
IE45759B1 true IE45759B1 (en) | 1982-11-17 |
Family
ID=5983513
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
IE1457/77A IE45759B1 (en) | 1976-07-16 | 1977-07-13 | Isomeric mixture of trimethylperhydroazepine -1- thiocarboxylic acid s-ethyl esters, process for the manufacture of this mixture and also its use as a herbicide |
Country Status (32)
Country | Link |
---|---|
JP (1) | JPS5312884A (en) |
AT (1) | AT360265B (en) |
AU (1) | AU512006B2 (en) |
BE (1) | BE856861A (en) |
BG (1) | BG32413A3 (en) |
BR (1) | BR7704670A (en) |
CA (1) | CA1096379A (en) |
CH (1) | CH631709A5 (en) |
CS (1) | CS192488B2 (en) |
DD (1) | DD130549A5 (en) |
DE (1) | DE2632676A1 (en) |
DK (1) | DK323777A (en) |
ES (1) | ES460670A1 (en) |
FI (1) | FI772096A (en) |
FR (1) | FR2358397A1 (en) |
GB (1) | GB1589681A (en) |
GR (1) | GR72096B (en) |
IE (1) | IE45759B1 (en) |
IL (1) | IL52498A (en) |
IT (1) | IT1077338B (en) |
LU (1) | LU77760A1 (en) |
NL (1) | NL7706148A (en) |
NO (1) | NO146094C (en) |
NZ (1) | NZ184574A (en) |
PL (1) | PL103046B1 (en) |
PT (1) | PT66813B (en) |
RO (1) | RO71240A (en) |
SE (1) | SE7708191L (en) |
SU (2) | SU691088A3 (en) |
TR (1) | TR19702A (en) |
YU (1) | YU152177A (en) |
ZA (1) | ZA774276B (en) |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1906050C3 (en) * | 1969-02-07 | 1979-01-25 | Basf Ag, 6700 Ludwigshafen | S-Alkyi-methyl-hexahydro-lHazepine) -1 -carbothiolate |
DE2152947A1 (en) * | 1970-10-24 | 1972-04-27 | Farbenfabriken Bayer Ag, 5090 Leverkusen | Selective herbicide for paddy fields - contg a 1-phenyl -3, 3-dimethyl-urea and a thiocarbamate |
DE2333397A1 (en) * | 1973-06-30 | 1975-01-23 | Basf Ag | CARBOTHIOLATE SUBSTITUTED AZEPINE |
-
1976
- 1976-07-16 DE DE19762632676 patent/DE2632676A1/en not_active Withdrawn
-
1977
- 1977-06-03 NL NL7706148A patent/NL7706148A/en not_active Application Discontinuation
- 1977-06-20 YU YU01521/77A patent/YU152177A/en unknown
- 1977-06-24 AU AU26444/77A patent/AU512006B2/en not_active Expired
- 1977-06-29 TR TR19702A patent/TR19702A/en unknown
- 1977-07-05 FI FI772096A patent/FI772096A/fi not_active Application Discontinuation
- 1977-07-06 NZ NZ184574A patent/NZ184574A/en unknown
- 1977-07-07 CA CA282,291A patent/CA1096379A/en not_active Expired
- 1977-07-07 BG BG7736830A patent/BG32413A3/en unknown
- 1977-07-11 IL IL52498A patent/IL52498A/en unknown
- 1977-07-11 GB GB28993/77A patent/GB1589681A/en not_active Expired
- 1977-07-12 ES ES460670A patent/ES460670A1/en not_active Expired
- 1977-07-12 CH CH861177A patent/CH631709A5/en not_active IP Right Cessation
- 1977-07-13 IE IE1457/77A patent/IE45759B1/en unknown
- 1977-07-14 AT AT508677A patent/AT360265B/en not_active IP Right Cessation
- 1977-07-14 SE SE7708191A patent/SE7708191L/en not_active Application Discontinuation
- 1977-07-14 DD DD200063A patent/DD130549A5/en unknown
- 1977-07-14 PL PL1977199634A patent/PL103046B1/en unknown
- 1977-07-14 LU LU77760A patent/LU77760A1/xx unknown
- 1977-07-14 GR GR53964A patent/GR72096B/el unknown
- 1977-07-14 RO RO7791036A patent/RO71240A/en unknown
- 1977-07-14 PT PT66813A patent/PT66813B/en unknown
- 1977-07-15 SU SU772502605A patent/SU691088A3/en active
- 1977-07-15 NO NO772525A patent/NO146094C/en unknown
- 1977-07-15 JP JP8493177A patent/JPS5312884A/en active Pending
- 1977-07-15 ZA ZA00774276A patent/ZA774276B/en unknown
- 1977-07-15 IT IT25806/77A patent/IT1077338B/en active
- 1977-07-15 BE BE179385A patent/BE856861A/en not_active IP Right Cessation
- 1977-07-15 BR BR7704670A patent/BR7704670A/en unknown
- 1977-07-15 SU SU772503100A patent/SU629852A3/en active
- 1977-07-15 DK DK323777A patent/DK323777A/en not_active Application Discontinuation
- 1977-07-18 FR FR7721931A patent/FR2358397A1/en active Granted
- 1977-07-18 CS CS774761A patent/CS192488B2/en unknown
Also Published As
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US4227009A (en) | Phenoxyphenoxy-propionic acid derivatives | |
US4927824A (en) | Fungicidal trisubstituted 1,3,5-triazine-2,4,6-triones | |
US4251263A (en) | N-substituted, 2-phenoxynicotinamide compounds and the herbicidal use thereof | |
CA2021919A1 (en) | 5-substituted 1,3,4-thiadiazole derivatives, their preparation and their use as pesticides | |
GB2043062A (en) | N-(heterocyclyl)-acetanilide derivatives and herbicidal and plant growth regulating compositions containing them | |
GB1583274A (en) | Herbicidally active benzodioxole derivatives process for their manufacture and their use | |
US3942971A (en) | Dithiophosphates and their use as herbicides | |
IL26698A (en) | Amidothionophosphoric acid ester | |
US2971884A (en) | Method for the control of fungal organisms | |
CS270566B2 (en) | Fungicide and method of its active substance production | |
IE45759B1 (en) | Isomeric mixture of trimethylperhydroazepine -1- thiocarboxylic acid s-ethyl esters, process for the manufacture of this mixture and also its use as a herbicide | |
US4626273A (en) | Herbicidal novel 2-alkoxyaminosulfonyl-benzene-sulfonylureas | |
US5064847A (en) | 5-substituted 3-arylisoxazole derivatives, their preparation and their use as pesticides | |
KR890003834B1 (en) | Process for oreoaring substituted maleimides | |
US4482737A (en) | Preparation of N-substituted N-isocyanatocarbonyl-carbamates | |
HU198185B (en) | Process for producing pyrazole derivatives | |
JP3163545B2 (en) | 4-thienyl-oxa (thia) azoline derivatives and insecticides and acaricides containing the same | |
US4159902A (en) | 1,3,3-Trimethyl-6-azabicyclo-(3.2.1)-octane-6-carboxylic acid ester, herbicides, process for making same and composition containing same | |
US5162351A (en) | Benzoisothiazoles, their preparation and their use as pesticides | |
US3758481A (en) | Ridine m-(2,4-dichloro - 5-(haloalkoxy)-phenylcarbomoyl)-pyrrolidine or pipe | |
US3989525A (en) | H-isopropyl-2-chloroethane-(thiono)-phosphonic acid ester amide compounds and herbicidal compositions | |
US4059430A (en) | Organic (thio) phosphoric acid ester compounds and herbicidal compositions | |
US3557150A (en) | Benzopyranyl carbamates | |
US3792168A (en) | Ethynylene containing n-phenyl carbamates and their use as acaricides and insecticides | |
IE45827B1 (en) | Selectively herbicidally active diurethanes, process for their manufacture and their use |