CA1100138A - Herbicidally active 1,3,3-trimethyl-6-azabicyclo-(3,2, 1)-octane-6-carboxylic acid esters and their manufacture and use - Google Patents
Herbicidally active 1,3,3-trimethyl-6-azabicyclo-(3,2, 1)-octane-6-carboxylic acid esters and their manufacture and useInfo
- Publication number
- CA1100138A CA1100138A CA282,400A CA282400A CA1100138A CA 1100138 A CA1100138 A CA 1100138A CA 282400 A CA282400 A CA 282400A CA 1100138 A CA1100138 A CA 1100138A
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- Prior art keywords
- compound
- octane
- trimethyl
- azabicyclo
- general formula
- Prior art date
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
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- Organic Chemistry (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Indole Compounds (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
The invention provides herbicidally active 1,3,3-tri-methyl-6-azabicyclo-(3,2,1)-octane-6-carboxylic acid esters of the general formula I
(I), in which R represents a radical selected from an alkyl containing 1 to 7 carbon atoms; an alkenyl containing 2 to 7 carbon atoms;
a phenyl which may be substituted with chlorine; and a phenyl alkyl wherein the alkyl group contains 1 to 4 carbon atoms and wherein the phenyl group may be substituted with chlorine.
and X and Y each represents an oxygen atom or a sulphur atom.
The invention provides herbicidally active 1,3,3-tri-methyl-6-azabicyclo-(3,2,1)-octane-6-carboxylic acid esters of the general formula I
(I), in which R represents a radical selected from an alkyl containing 1 to 7 carbon atoms; an alkenyl containing 2 to 7 carbon atoms;
a phenyl which may be substituted with chlorine; and a phenyl alkyl wherein the alkyl group contains 1 to 4 carbon atoms and wherein the phenyl group may be substituted with chlorine.
and X and Y each represents an oxygen atom or a sulphur atom.
Description
The present i~n~ention is concerned with new herbicidally acti~e lr3~3 t~imethyl,6~azabicyclo (3r2 !1) octane~6-carbo~ylic acid esters, with ~rocesses for their manu~acture and also wlth their use.
It has alreadv been known that alkyleneiminocarbothio~
lates are herbicidally actIve (United States patent Specification No. 3~198~786), However, these compounds develop sufficient selec~ive-herbicidal properties only in certain crops o~ useful plants, for exam,le in rice crops for combating Echinochloa sp~
The present i,n~ention provides an aaent of the kind in question, which has a wIde spectrum of selectivity towards crop plants and a very good herbicidal action against weeds.
According to the present invention, there is provided com~ounds of the general formula I
c~3 C I 2 ~ ~ ~H2 H C ~ ~ C-~-R (I),
It has alreadv been known that alkyleneiminocarbothio~
lates are herbicidally actIve (United States patent Specification No. 3~198~786), However, these compounds develop sufficient selec~ive-herbicidal properties only in certain crops o~ useful plants, for exam,le in rice crops for combating Echinochloa sp~
The present i,n~ention provides an aaent of the kind in question, which has a wIde spectrum of selectivity towards crop plants and a very good herbicidal action against weeds.
According to the present invention, there is provided com~ounds of the general formula I
c~3 C I 2 ~ ~ ~H2 H C ~ ~ C-~-R (I),
2~ J~
X
in which R represents a radical selected from an alkyl containing l to 7 carbon atoms; an alkenyl containing 2 to 7 carbon atoms;
a phenyl which may be substituted with chlorine; and a phenyl alkyl wherein the alkyl ~roup contains l to ~ carbon atoms and wherein the phenyl group may be substituted with chlorine.
:
-2- ~
and X and Y each represents an oxvgen atom or a sulphur atom.
The co~pounds gf the present invention are distin~uished by an outstanding herbicidal action esPecia11y agaInst mono-cotyledonous weeds~ for example Avena, Alo~ecurus, Echinochloa c.~.~ Setar1~a~ DIgltaria, Poa! Hordeum and Triticum.
Owin~ to their excellent selective properties they can be used in agxicultural crops, for example in cauliflower, beetroot, tomato, bush bean, soya bean, cotton and rice crops.
The compounds of the present invention can also be used in maize and sorah~m, ~t heing advantaaeous to admix an antidote, for example 8-naphthalic anhydride or N,N-diallyl-dichloracetamide, with the seed grain or the s~raying preparation, respectively.
A further advantage of the compounds of the present invention is that they also possess growth-reaulating properties.
The compounds act satisfactorilY even at rates of application from 1 k$ of active substance per hectare, and, owing to their surprisinaly wide spectrum of selectivity, they can be used withou~ injuring crops of useful plants in auantities of ~` up to 8 kq of active substance per hectare before sowing by incorporation in the soil; when two or more compounds of the general formula I are used the range of 1 to 8 kg refers of course to the total amount used of these compounds.
The PreSent i-nvention accordinglv also provides a herblcidal preparation which comprises a compound of the general formula I, in a~mixture or conjunction with a suitable carr~er~ The preparation ~lay of course contain one .
X
in which R represents a radical selected from an alkyl containing l to 7 carbon atoms; an alkenyl containing 2 to 7 carbon atoms;
a phenyl which may be substituted with chlorine; and a phenyl alkyl wherein the alkyl ~roup contains l to ~ carbon atoms and wherein the phenyl group may be substituted with chlorine.
:
-2- ~
and X and Y each represents an oxvgen atom or a sulphur atom.
The co~pounds gf the present invention are distin~uished by an outstanding herbicidal action esPecia11y agaInst mono-cotyledonous weeds~ for example Avena, Alo~ecurus, Echinochloa c.~.~ Setar1~a~ DIgltaria, Poa! Hordeum and Triticum.
Owin~ to their excellent selective properties they can be used in agxicultural crops, for example in cauliflower, beetroot, tomato, bush bean, soya bean, cotton and rice crops.
The compounds of the present invention can also be used in maize and sorah~m, ~t heing advantaaeous to admix an antidote, for example 8-naphthalic anhydride or N,N-diallyl-dichloracetamide, with the seed grain or the s~raying preparation, respectively.
A further advantage of the compounds of the present invention is that they also possess growth-reaulating properties.
The compounds act satisfactorilY even at rates of application from 1 k$ of active substance per hectare, and, owing to their surprisinaly wide spectrum of selectivity, they can be used withou~ injuring crops of useful plants in auantities of ~` up to 8 kq of active substance per hectare before sowing by incorporation in the soil; when two or more compounds of the general formula I are used the range of 1 to 8 kg refers of course to the total amount used of these compounds.
The PreSent i-nvention accordinglv also provides a herblcidal preparation which comprises a compound of the general formula I, in a~mixture or conjunction with a suitable carr~er~ The preparation ~lay of course contain one .
3-l3l~
, or more cornpounds of the c~e~llerai formula I.
Tlle present invention further provides a method of protec-ting a living plant against weeds, wherein the area in the vicinity of tlle living plant is treated wi-th a compound of the general formula I.
Tne present invention furkher provides a method of protecting a crop area against weeds, w~erein the crop area is treated with a compound of -the general formula I.
Tlle present invention further provides a pack which comprises a compound of the general formula I together with instruc-tions for its use as a herbicide.
The compounds of thepresent invention can be used either alone or in admix-ture with one anotner or with other active substances.
In this connection, depending of -the purpose desired, there may be mentioned, for e~ample, the following herbicidally active substances, which, if desired, may be added to the compounds o the present invention only immediately before use:
substituted anilines, substituted aryloxy-carboxylic acids and also salts, esters and amides tilereof, substituted ethers, substituted arsonic acids and also salts, esters and amides tllereof, .' substituted benzimidazoles, su~stltuted benzisothiazoles, .
31~3 substi.~uted bellzt-liadidzinorle dio~i.des, substituted benzoxazines, substituted benzo~azinones, substituted benzthiazoles, substituted benz-thiadiazines, substituted biurets, substi-tuted quinoline5, substituted carbamates, substituted aliphatic carboxylic acids and also salts, ex-ters and amides thereof, ; substitu-ted aromatic carboxylic acids and also salts, esters and amides thereof, substituted carbamoylalkyl--thio- or dithio-phosphates, substituted ~uinazolines, substituted cyc]oalkylamidocarbonthiolic acids and also salts, esters and amides thereof, substituted cycloalkylcarbonamido-thiazoles, substituted dicarboxylic acids and also salts, esters and amides thereof, substituted ai~lydrobenzofuranyl sulphonates, substituted disulphides, substituted dipyridylium salts, substituted ditiliocarbamates, substituted dithiopnosphoric acids and also salts, esters and amides thereof, substituted ureas, substituted hexallydro-lll-carbothioates, ' .
: ~ - 5 -substi-Luted hyclantoins substituted hydrazides substituted hydrazonium salts, substituted isoxazolepyrimidones substituted ;midazoles, substituted isothiazolepyrimidones, substitu-ted ketones, suhstituted napllthoqui.nones, substituted aliphatic nitriles, subs-cituted aromatic nitriles, substituted oxadiazoles, ubstituted oxadiazinones, substituted oxadiazolidinediones, su~stituted oxadiazinediones, substituted phenols and also salts and esters thereof, substituted phosphonic acids and also salts, esters and amides thereo~
substituted phosphonium clllorides, substituted phosphonalkylglycines, substituted phosphites, substituted phosphoric acids and also salts esters and amides thereof, substituted piperidines suhstituted pyrazoles substituted pyrazolalkylcarboxylic acids and also salts, esters : and amides thereof, substituted pyrazo]ium salts, ~ - 6 ~
substituted pyrazolium alkyl sulpha-tes, substituted pyridazines, substituted pyridazones, substituted pyridine carboxylic acids and also salts, esters and amides ~hereof, substituted pyridirles, substituted pyridine carboxylates, substituted pyridinones, substituted pyrimidones, substituted pyrolidine 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, substituted tetrahydro-thiadiazine-thiones, substituted tetrahydro-thiadiazolediones, 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, ~ _ 7 _ 3~
substituted triazines, subs-tituted triazoles, substituted uracils and substituted uretidlnedioneS.
Furthermore, there may be used o-ther additives, for example non-phytotoxic adaitives, which impart -to herbicides a synergistic increase in action, for examp]e wetting agents, emulsifiers, solvents and oily additives.
The characterized active substances or mixtures thereof are advantageously used in the form of herbicidal preparations, for example powders, strewable preparations, granules, solutions, emulsions, and suspensions, with the addition of liquid and/or solid verhicles or diluents, and if desired, of surface-active agents, for example wetting, adherent, emulsifying and/or dispersiny agents.
Suitable liquid carriers are, for example water, aliphat hydrocarbons, aromatic hydrocarbons, for example benzene, toluene and xylene, cyclohexanone, isophorone, dimethyl sulphoxide and dimethylEormamide, and also mineral oil fractions.
0 ~s solid carriers tilere 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, polyoxye-thylenalkyl-phenyl ethers, naphthalene sulphonic acids and salts thereof, phenol .
..
sulphonic acids and salts thereo*~ formaldeh~de condensates~
~atty alcohol sulphates and also substituted benzene sulphonic acids and salts thereof.
The total propor-tion of the active substance or substances in the various herbicidal preparations ~av varv wIthin wide limits. ~or example~ the preparations may contain approximatelv 10 to 80% by weiyht of active compound(s), approximately 90 to 20% hy weiaht o~ liquid or solid carrier and also, if desired~ up to 20% by weight of surface-active agent~s).
The active compounds may be applied in the usual manner, for example with water as carrier in quantities of spray liuor from approximately 100 to 1000 litres per hectare. It is also possible to apply the active compounds by the so-called "low yolumel' and "ultra-low volume" methods and also to apply the,m in the *orm of so-called micro~ranules.
3~
Grou~s represented by R there are preferably mentioned amonast:many! f~r examnle~ ~ethyl~ ethyl, propyl~ isopropyl, allyl~ but~l~ sec.~butyl, isobutyl, tert.-.butyl, buten~l, Penty i$opentyl~ benzvl~ 4-chlorobenzYl, 2,4-dichlorobenzyl~ phenyl and 4-~chlorophenvl aroups.
The new compounds of the general formula I may be prepared, for example, by the process of the present inVention~
as defined below.
The present invention accordingly further provides a process for the manufacture of a compound of the general formula I, wherein 1,3,3-trimethyl-6-azabicyclo-(3,2,1)-octane of the formula ~H3 ~Hz~ C _ -- CH
~I3C I I i ~~ IH2 NH
2~ CH-if desired dissolved in a solvent, (a) is reacted, if aesired in the presence of an acid-binding agent, with a halogeno formic acid ester of the general formula Hal~C-Y-R
in which R~ X ahd~Y have the meanings given above .
~10-.. . .. .
.
L3~
and l-lal represents a halogen a-tom, or ~i~) is react~2cl ill t]le L~resence of a base with a compound of -the general forrnula X = C = Y, ; in which X and Y have the meanings yiven above, to form a salt of s~ch a base of the yeneral formula cr~
: ~ 3 : ~ C 1 2 1 CH~
~ C CH
H3C ~ C Y(-)B(~ 3 . ` X
in -~hicll X and ~ have t'le meaning~ give:l 3bove and ~ r~p.~e~ei-ts ~ c~tion ~e~ ed from t'ne '.~ase, and the salt is treated witn an akylating agent of the general formula 1~- z, in which R has -tlle meaning yiven above and Z represents a halogen atom, an alkyl sulphuric acid group or a toluene sulphonic acid group, or (c) is reacted witn a ~hosgene com-~ound of tile general formula Hal2C = X j in which X and Hal 1~ave the meanings given above to form a l,3,3-trimethyl--6-azabicyclo-(3,Z,l)-octane-6-carboxylic acid llalide of the general formula l~3 CI~2_ C C~l 113C ~ ¦ I N-C-Hal C~2~. CI~ X
in ~.~hicl~ X and Hal have the meanings givell above, wllicil is tiiell reacted witll an oxygen- or thio-compourld of -the general formula R-Y( )B( ) in whi.ch R and Y nave the meanings given above and B( ) represents a cation.
3~3 The presen-t invention also includes within its scope a process for the manufacture of a compound of the yeneral formula I, wherein a 1,3,3-trimethyl-6-azabicyclo-(3,2,1)-octane-6-carboxylic acid halide of the general forrnula sho~n in the definition of variant (c) of the process defined above, in which X and Hal llave t~le meanings given above, is reacted with an oxygen- or thio-compound of the general forrnula R - Y( )B( ) in which R, Y and s(+) have the rneanings given above.
'0 As bases or acid-binding ayents, respectively, 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 N,N-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. An excess of the liquid starting base used may also function as acid-binding agent.
As al~ylating agents there are advantageously used chlorides, bromides and iodides.
The reaction of the components is carried out at between 0 and 12~C., but generally at room temperature.
For the synthesis of the compounds of the present invention the reactants are used in approximately equimolar quantities.
Suitable reaction media are solven-ts inert towards the reactants, either alone or in admixtuxe with water. Amongst many such reaction media the following rnay be mentioned by way of example, namely aliphatic aromatic hydrocarbons, ~or examE~le, petroleum ether, cyclohexane, benæene, toluene and xylene, halogenated hydrocarbons, for example me-thylene chloride, chloroform, carbon tetrachloride and ha]ogenated ethylenes, ether-like compounds, for example diethyl ether, diisopropyl _ -. ' . : ' 3i~3 e-ther, tetrallydrofuran and dioxane, ketones, ~or example ace-tone, :~ methyl isobutyl ]cetone and isophorone, esters, for example methyl and ethyl acetate, acid amides, for example dimethyl-: ~ormamide and hexamethylphosphoric acid triamide, and carboxylic acid nitriles, for example acetonitrile.
. . Finally, the iso]ation of the compounds of -the present inven-tion may be carried out in a manner known per se by distilling off the solvent or extraction medium used under atmospheric or reduced pressure, optionally after treatmen-t with O acid or basic agents to remove undesired by-products. If necessary, the compounds may be distilled ln vacuo for purification.
Tlle starting compounds used for preparing the compounds of the present invention are known or can be prepared by methods known er se.
Some specific compounds of the present invention are~
listed in the ~ollowing Table:
TABLE
Name of the compound Physial constant _ .0 1,3,3~Trimethyl-6-azabicyclo-(3,2,1)-octane-6-thiocarboxylic acid S-ethyl - 20 èster nD = 1.5123 1,3,3-Trimethyl-6-azabicyclo-(3,2,1)-octane-6-dithiocarboxylic acid (2- 20 pro~enyl)ester nD = 1.5810 1,3,3-Trimethyl-6-azabicyclo--(3,2,1)- 20 .
octane-6-carboxylic acid methyl ester nD = 1.48 - 1,3,3-Trimethyl-6-azabicyclo-(3,2,1)-octane-6-tlliocarboxylic aci.d S-~lethyl 20 ester nD = 1.5J72 1,3,3-Trimethyl-6-azabicyclo-(3,2,].)-octane--6-thiocarboxylic acid S-propyl 20 ester nD = 1.5090 1,3,3-Trimethyl-6-azabicyclo-(3,2,1.)-octane-6-thiocarboxylic acid S-benzyl 20 ester nD = 1.5526 l~3~3-Trimethyl-6-azabicyclo-(3l2~l)- 20 octane-6-carboxylic acid ethy:L ester nD -~ 1.4702 ~ ~ 13 -Name of the compoulld Physical constant 1,3,3-Trimethyl-6-azabicyclo-(3,2,1)- 20 octane-6--carboxylic acid propyl ester n~ = 1.4692 1,3,3-Trimethyl-6-azabicyclo-(3,2,1)- 20 octane-6-carboxylic acid butyl es-ter nD = 1.4612 1,3,3-Trimethyl-6-azabicyc]o-(3,2,1)- 20 octane-6-carhoxylic acid isopropyl ester nD = ] 4652 1,3,3-Trimethyl-6-azal~icyclo-(3,2,1)-octane-6-carboxylic acid ~2-propenyl) 20 ester nD = 1.4796 1,3,3-Trimethyl-6-azabicyclo-(3,2,1)- 20 octane-6-carboxylic acid phenyl ester nD = 1.5224 1,3,3-Trimethyl-6-azabicyclo-(3,2,1)-octant-6-thiocarboxylic acid S-(4- 2 fluorophenyl) ester nD = 1.5488 1,3,3-Trimethyl-6-azabicyclo-(3,2,1)- 20 octane-6-carboxylic acid benzyl ester nD = 1.5212 1,3,3-Trimethyl-6-azabicyclo-(3,2,1)- 2 octane-6-carboxylic acid pentyl ester nD = 1.4664 The compounds of the present invention are colourless or slightly yellow coloured oils having a slight aromatic odour, which are insoluble in water, but readily dissolve in all organic solvents, for example hydrocarbons, halogenated hydro-carbons, ethers, ketones, carboxylic acid esters, carboxylic acid amides, carboxylic acid nitriles, alcohols, carbo~ylic acids, sulphoxides and many others.
The following Examples illustrate the invention.
Examples 1 to 3 illustrate the manufacture of the compounds of the present in-vention and Examples 4 and 5 illustrate the possibilities of use of the compounds of -the pre.sent invention.
x;-mp.e 1 ~ o a solu-tion of 61.3 gms of 1,3,3-trimetllyl-6-azabicyclo-(3,2,1)-octane in 150 ml of diisopropyl ether were s]owly added dropwise, while stirring, 24.9 gms of chloro--thioformic acid S-e-thyl ester at room temper~ture. After being stirred for one hour the reaction mixture was extracted by agitation wi-th water, then dilute hydrochloric acid and ayain with water, the oryanic .: :
..
phase was dried over magnesium sulphate, the so]vent was distilled off ~n vacuo and finally the mix-ture was freed ~rom the residual solvent in a high vacuum.
sy adding sodium h~droxide solution to the first water extract the excess of starting material used was recovered.
Yield: ~6.0 Gms (95.29% of theoretical yie]d) of 1~3/3-trimethyl-6-azabicyclo-(3r2/l)-octane-6-thiocarboxylic acid S-ethyl ester o* nD - 1.5123.
Analysis: Calculated C 64.68% H 9.60% N 5.80%
Found C 64.38% H 9.65% N 6.01%
Example 2 Into a mixture of 34 ml of 1,3,3-trimethyl-6-azabicyclo-(3,2,1)-octane, 50 ml of acetonitrile and 8 gms of sodium hydroxide dissolved in 50 ml of water, were added dropwise, while stirring, at between 10 and 15C. ]5.2 gms of carbon disulphide. To form the dithiocarbamic acid salt the mixture was stirred for a further 2 hours~ There were then added dropwise to the reaction mlxture 24.5 gms of allyl bromide, and the whole was stirred for one hour for ester formation. After the addition of 500 ml of methylene chloride, the organic phase was extracted by agitation with hydrochloric acid, dried ovér magnesium sulphate, treated with active carbon and concentrated in a high vacuum.
Tllere remained behilld 52 yms (96.4% of theoretical yield) of 1,3,3-trimetllyl-6-azabicyclo-(3,2,1)-octane-6-ditiliocar~oxylic aci~
allyl ester of n20 = 1.5810. -Anal~sis: Calculated C 62.40% H 8.60% N 5.20% S 23.80%
Found C 62.23% H 8.53% N 5.02% S 23.71%
Example 3 Into a solu-tion of 21.5 gms of 1,3,5-trimethyl-6-azabicyclo-(3,2,:L)-octane-6 car~oxylic acid chloride in 100 ml of acetonitrile were introcluced, while stirring, 5.4 yms of sodium methylate. After ~eing stirred for two hours, there were . ",;
.
3~
added to the reaction mixture 350 ml of ~ater, the oil -that separated was extracted wi-th cllloroform, the chloroform phase was extracted by agitation wi-th dilute hydrochloric acid, then dried over magnesium sulphate, and finall.y the solvent was distilled off in a high vacuum. There remained behind 19.0 ~ms (90.~% of the theoretical yield) of oily 1,3,5-trirnethyl-6-azabicyclo-(3/2/l)--octane-6-cal-boxylic acid me-thyl ester having n20 = 1.4840.
Analysis: Calculated C 68.21% H 10.02% N 6.63~
Found C 68.23% H 10.01~ N 7.03%
Each of the other compounds of the present invention listed in the Table above can be prepared in a manner analogous to that described in any one of Examples 1 to 3 Ex m le 4 In a series of tests carried out in a greenhouse the compounds of the present invention listed in the Table below were each sprayed at a rate of application of 5 kg of active substance per hectare, suspended in 500 litres of water per hectare, onto the soil before the sowing of _olium and Setaria and worked into the soil. Three weeks after the treatment the results thereof were evaluated, the results being expressed by a numerical scale extendiny from 0 to 4, the value 0 representing ..
no action and the value 4 representing destruction of the plant.
Compound of the present invention Lolium Setaria 1,3,3-Trimethyl-6-azabicyclo-(3,2,1)-octane-6-thiocarboxylic acid S--e-thyl . -.
ester ~ 4 1,3,3-Trimetilyl-6-- azabicyclo-¦3,2,1)-octane-6-thiocarbo~yllc acid S-methyl ester 4 1,3,3-Trimethyl-6--azahicyclo-(3,2,1)-octane-6-t]liocarboxylic acid S-propyl ester 4 ~G10~3~
Compoulld of the i nv en-tion ~,o.lium Set_rla 1,3,3-Trimethyl-6- ~zabicyclo-(3,2,1)-octane-G-dithiocarboxylic acid (2-propenyl) ester 4 3 1,3,3-Trimethyl-6-azabicyclo-(3,2,1)-octane-6-thiocarboxylic acid S-benzyl ester 3 O = no action
, or more cornpounds of the c~e~llerai formula I.
Tlle present invention further provides a method of protec-ting a living plant against weeds, wherein the area in the vicinity of tlle living plant is treated wi-th a compound of the general formula I.
Tne present invention furkher provides a method of protecting a crop area against weeds, w~erein the crop area is treated with a compound of -the general formula I.
Tlle present invention further provides a pack which comprises a compound of the general formula I together with instruc-tions for its use as a herbicide.
The compounds of thepresent invention can be used either alone or in admix-ture with one anotner or with other active substances.
In this connection, depending of -the purpose desired, there may be mentioned, for e~ample, the following herbicidally active substances, which, if desired, may be added to the compounds o the present invention only immediately before use:
substituted anilines, substituted aryloxy-carboxylic acids and also salts, esters and amides tilereof, substituted ethers, substituted arsonic acids and also salts, esters and amides tllereof, .' substituted benzimidazoles, su~stltuted benzisothiazoles, .
31~3 substi.~uted bellzt-liadidzinorle dio~i.des, substituted benzoxazines, substituted benzo~azinones, substituted benzthiazoles, substituted benz-thiadiazines, substituted biurets, substi-tuted quinoline5, substituted carbamates, substituted aliphatic carboxylic acids and also salts, ex-ters and amides thereof, ; substitu-ted aromatic carboxylic acids and also salts, esters and amides thereof, substituted carbamoylalkyl--thio- or dithio-phosphates, substituted ~uinazolines, substituted cyc]oalkylamidocarbonthiolic acids and also salts, esters and amides thereof, substituted cycloalkylcarbonamido-thiazoles, substituted dicarboxylic acids and also salts, esters and amides thereof, substituted ai~lydrobenzofuranyl sulphonates, substituted disulphides, substituted dipyridylium salts, substituted ditiliocarbamates, substituted dithiopnosphoric acids and also salts, esters and amides thereof, substituted ureas, substituted hexallydro-lll-carbothioates, ' .
: ~ - 5 -substi-Luted hyclantoins substituted hydrazides substituted hydrazonium salts, substituted isoxazolepyrimidones substituted ;midazoles, substituted isothiazolepyrimidones, substitu-ted ketones, suhstituted napllthoqui.nones, substituted aliphatic nitriles, subs-cituted aromatic nitriles, substituted oxadiazoles, ubstituted oxadiazinones, substituted oxadiazolidinediones, su~stituted oxadiazinediones, substituted phenols and also salts and esters thereof, substituted phosphonic acids and also salts, esters and amides thereo~
substituted phosphonium clllorides, substituted phosphonalkylglycines, substituted phosphites, substituted phosphoric acids and also salts esters and amides thereof, substituted piperidines suhstituted pyrazoles substituted pyrazolalkylcarboxylic acids and also salts, esters : and amides thereof, substituted pyrazo]ium salts, ~ - 6 ~
substituted pyrazolium alkyl sulpha-tes, substituted pyridazines, substituted pyridazones, substituted pyridine carboxylic acids and also salts, esters and amides ~hereof, substituted pyridirles, substituted pyridine carboxylates, substituted pyridinones, substituted pyrimidones, substituted pyrolidine 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, substituted tetrahydro-thiadiazine-thiones, substituted tetrahydro-thiadiazolediones, 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, ~ _ 7 _ 3~
substituted triazines, subs-tituted triazoles, substituted uracils and substituted uretidlnedioneS.
Furthermore, there may be used o-ther additives, for example non-phytotoxic adaitives, which impart -to herbicides a synergistic increase in action, for examp]e wetting agents, emulsifiers, solvents and oily additives.
The characterized active substances or mixtures thereof are advantageously used in the form of herbicidal preparations, for example powders, strewable preparations, granules, solutions, emulsions, and suspensions, with the addition of liquid and/or solid verhicles or diluents, and if desired, of surface-active agents, for example wetting, adherent, emulsifying and/or dispersiny agents.
Suitable liquid carriers are, for example water, aliphat hydrocarbons, aromatic hydrocarbons, for example benzene, toluene and xylene, cyclohexanone, isophorone, dimethyl sulphoxide and dimethylEormamide, and also mineral oil fractions.
0 ~s solid carriers tilere 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, polyoxye-thylenalkyl-phenyl ethers, naphthalene sulphonic acids and salts thereof, phenol .
..
sulphonic acids and salts thereo*~ formaldeh~de condensates~
~atty alcohol sulphates and also substituted benzene sulphonic acids and salts thereof.
The total propor-tion of the active substance or substances in the various herbicidal preparations ~av varv wIthin wide limits. ~or example~ the preparations may contain approximatelv 10 to 80% by weiyht of active compound(s), approximately 90 to 20% hy weiaht o~ liquid or solid carrier and also, if desired~ up to 20% by weight of surface-active agent~s).
The active compounds may be applied in the usual manner, for example with water as carrier in quantities of spray liuor from approximately 100 to 1000 litres per hectare. It is also possible to apply the active compounds by the so-called "low yolumel' and "ultra-low volume" methods and also to apply the,m in the *orm of so-called micro~ranules.
3~
Grou~s represented by R there are preferably mentioned amonast:many! f~r examnle~ ~ethyl~ ethyl, propyl~ isopropyl, allyl~ but~l~ sec.~butyl, isobutyl, tert.-.butyl, buten~l, Penty i$opentyl~ benzvl~ 4-chlorobenzYl, 2,4-dichlorobenzyl~ phenyl and 4-~chlorophenvl aroups.
The new compounds of the general formula I may be prepared, for example, by the process of the present inVention~
as defined below.
The present invention accordingly further provides a process for the manufacture of a compound of the general formula I, wherein 1,3,3-trimethyl-6-azabicyclo-(3,2,1)-octane of the formula ~H3 ~Hz~ C _ -- CH
~I3C I I i ~~ IH2 NH
2~ CH-if desired dissolved in a solvent, (a) is reacted, if aesired in the presence of an acid-binding agent, with a halogeno formic acid ester of the general formula Hal~C-Y-R
in which R~ X ahd~Y have the meanings given above .
~10-.. . .. .
.
L3~
and l-lal represents a halogen a-tom, or ~i~) is react~2cl ill t]le L~resence of a base with a compound of -the general forrnula X = C = Y, ; in which X and Y have the meanings yiven above, to form a salt of s~ch a base of the yeneral formula cr~
: ~ 3 : ~ C 1 2 1 CH~
~ C CH
H3C ~ C Y(-)B(~ 3 . ` X
in -~hicll X and ~ have t'le meaning~ give:l 3bove and ~ r~p.~e~ei-ts ~ c~tion ~e~ ed from t'ne '.~ase, and the salt is treated witn an akylating agent of the general formula 1~- z, in which R has -tlle meaning yiven above and Z represents a halogen atom, an alkyl sulphuric acid group or a toluene sulphonic acid group, or (c) is reacted witn a ~hosgene com-~ound of tile general formula Hal2C = X j in which X and Hal 1~ave the meanings given above to form a l,3,3-trimethyl--6-azabicyclo-(3,Z,l)-octane-6-carboxylic acid llalide of the general formula l~3 CI~2_ C C~l 113C ~ ¦ I N-C-Hal C~2~. CI~ X
in ~.~hicl~ X and Hal have the meanings givell above, wllicil is tiiell reacted witll an oxygen- or thio-compourld of -the general formula R-Y( )B( ) in whi.ch R and Y nave the meanings given above and B( ) represents a cation.
3~3 The presen-t invention also includes within its scope a process for the manufacture of a compound of the yeneral formula I, wherein a 1,3,3-trimethyl-6-azabicyclo-(3,2,1)-octane-6-carboxylic acid halide of the general forrnula sho~n in the definition of variant (c) of the process defined above, in which X and Hal llave t~le meanings given above, is reacted with an oxygen- or thio-compound of the general forrnula R - Y( )B( ) in which R, Y and s(+) have the rneanings given above.
'0 As bases or acid-binding ayents, respectively, 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 N,N-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. An excess of the liquid starting base used may also function as acid-binding agent.
As al~ylating agents there are advantageously used chlorides, bromides and iodides.
The reaction of the components is carried out at between 0 and 12~C., but generally at room temperature.
For the synthesis of the compounds of the present invention the reactants are used in approximately equimolar quantities.
Suitable reaction media are solven-ts inert towards the reactants, either alone or in admixtuxe with water. Amongst many such reaction media the following rnay be mentioned by way of example, namely aliphatic aromatic hydrocarbons, ~or examE~le, petroleum ether, cyclohexane, benæene, toluene and xylene, halogenated hydrocarbons, for example me-thylene chloride, chloroform, carbon tetrachloride and ha]ogenated ethylenes, ether-like compounds, for example diethyl ether, diisopropyl _ -. ' . : ' 3i~3 e-ther, tetrallydrofuran and dioxane, ketones, ~or example ace-tone, :~ methyl isobutyl ]cetone and isophorone, esters, for example methyl and ethyl acetate, acid amides, for example dimethyl-: ~ormamide and hexamethylphosphoric acid triamide, and carboxylic acid nitriles, for example acetonitrile.
. . Finally, the iso]ation of the compounds of -the present inven-tion may be carried out in a manner known per se by distilling off the solvent or extraction medium used under atmospheric or reduced pressure, optionally after treatmen-t with O acid or basic agents to remove undesired by-products. If necessary, the compounds may be distilled ln vacuo for purification.
Tlle starting compounds used for preparing the compounds of the present invention are known or can be prepared by methods known er se.
Some specific compounds of the present invention are~
listed in the ~ollowing Table:
TABLE
Name of the compound Physial constant _ .0 1,3,3~Trimethyl-6-azabicyclo-(3,2,1)-octane-6-thiocarboxylic acid S-ethyl - 20 èster nD = 1.5123 1,3,3-Trimethyl-6-azabicyclo-(3,2,1)-octane-6-dithiocarboxylic acid (2- 20 pro~enyl)ester nD = 1.5810 1,3,3-Trimethyl-6-azabicyclo--(3,2,1)- 20 .
octane-6-carboxylic acid methyl ester nD = 1.48 - 1,3,3-Trimethyl-6-azabicyclo-(3,2,1)-octane-6-tlliocarboxylic aci.d S-~lethyl 20 ester nD = 1.5J72 1,3,3-Trimethyl-6-azabicyclo-(3,2,].)-octane--6-thiocarboxylic acid S-propyl 20 ester nD = 1.5090 1,3,3-Trimethyl-6-azabicyclo-(3,2,1.)-octane-6-thiocarboxylic acid S-benzyl 20 ester nD = 1.5526 l~3~3-Trimethyl-6-azabicyclo-(3l2~l)- 20 octane-6-carboxylic acid ethy:L ester nD -~ 1.4702 ~ ~ 13 -Name of the compoulld Physical constant 1,3,3-Trimethyl-6-azabicyclo-(3,2,1)- 20 octane-6--carboxylic acid propyl ester n~ = 1.4692 1,3,3-Trimethyl-6-azabicyclo-(3,2,1)- 20 octane-6-carboxylic acid butyl es-ter nD = 1.4612 1,3,3-Trimethyl-6-azabicyc]o-(3,2,1)- 20 octane-6-carhoxylic acid isopropyl ester nD = ] 4652 1,3,3-Trimethyl-6-azal~icyclo-(3,2,1)-octane-6-carboxylic acid ~2-propenyl) 20 ester nD = 1.4796 1,3,3-Trimethyl-6-azabicyclo-(3,2,1)- 20 octane-6-carboxylic acid phenyl ester nD = 1.5224 1,3,3-Trimethyl-6-azabicyclo-(3,2,1)-octant-6-thiocarboxylic acid S-(4- 2 fluorophenyl) ester nD = 1.5488 1,3,3-Trimethyl-6-azabicyclo-(3,2,1)- 20 octane-6-carboxylic acid benzyl ester nD = 1.5212 1,3,3-Trimethyl-6-azabicyclo-(3,2,1)- 2 octane-6-carboxylic acid pentyl ester nD = 1.4664 The compounds of the present invention are colourless or slightly yellow coloured oils having a slight aromatic odour, which are insoluble in water, but readily dissolve in all organic solvents, for example hydrocarbons, halogenated hydro-carbons, ethers, ketones, carboxylic acid esters, carboxylic acid amides, carboxylic acid nitriles, alcohols, carbo~ylic acids, sulphoxides and many others.
The following Examples illustrate the invention.
Examples 1 to 3 illustrate the manufacture of the compounds of the present in-vention and Examples 4 and 5 illustrate the possibilities of use of the compounds of -the pre.sent invention.
x;-mp.e 1 ~ o a solu-tion of 61.3 gms of 1,3,3-trimetllyl-6-azabicyclo-(3,2,1)-octane in 150 ml of diisopropyl ether were s]owly added dropwise, while stirring, 24.9 gms of chloro--thioformic acid S-e-thyl ester at room temper~ture. After being stirred for one hour the reaction mixture was extracted by agitation wi-th water, then dilute hydrochloric acid and ayain with water, the oryanic .: :
..
phase was dried over magnesium sulphate, the so]vent was distilled off ~n vacuo and finally the mix-ture was freed ~rom the residual solvent in a high vacuum.
sy adding sodium h~droxide solution to the first water extract the excess of starting material used was recovered.
Yield: ~6.0 Gms (95.29% of theoretical yie]d) of 1~3/3-trimethyl-6-azabicyclo-(3r2/l)-octane-6-thiocarboxylic acid S-ethyl ester o* nD - 1.5123.
Analysis: Calculated C 64.68% H 9.60% N 5.80%
Found C 64.38% H 9.65% N 6.01%
Example 2 Into a mixture of 34 ml of 1,3,3-trimethyl-6-azabicyclo-(3,2,1)-octane, 50 ml of acetonitrile and 8 gms of sodium hydroxide dissolved in 50 ml of water, were added dropwise, while stirring, at between 10 and 15C. ]5.2 gms of carbon disulphide. To form the dithiocarbamic acid salt the mixture was stirred for a further 2 hours~ There were then added dropwise to the reaction mlxture 24.5 gms of allyl bromide, and the whole was stirred for one hour for ester formation. After the addition of 500 ml of methylene chloride, the organic phase was extracted by agitation with hydrochloric acid, dried ovér magnesium sulphate, treated with active carbon and concentrated in a high vacuum.
Tllere remained behilld 52 yms (96.4% of theoretical yield) of 1,3,3-trimetllyl-6-azabicyclo-(3,2,1)-octane-6-ditiliocar~oxylic aci~
allyl ester of n20 = 1.5810. -Anal~sis: Calculated C 62.40% H 8.60% N 5.20% S 23.80%
Found C 62.23% H 8.53% N 5.02% S 23.71%
Example 3 Into a solu-tion of 21.5 gms of 1,3,5-trimethyl-6-azabicyclo-(3,2,:L)-octane-6 car~oxylic acid chloride in 100 ml of acetonitrile were introcluced, while stirring, 5.4 yms of sodium methylate. After ~eing stirred for two hours, there were . ",;
.
3~
added to the reaction mixture 350 ml of ~ater, the oil -that separated was extracted wi-th cllloroform, the chloroform phase was extracted by agitation wi-th dilute hydrochloric acid, then dried over magnesium sulphate, and finall.y the solvent was distilled off in a high vacuum. There remained behind 19.0 ~ms (90.~% of the theoretical yield) of oily 1,3,5-trirnethyl-6-azabicyclo-(3/2/l)--octane-6-cal-boxylic acid me-thyl ester having n20 = 1.4840.
Analysis: Calculated C 68.21% H 10.02% N 6.63~
Found C 68.23% H 10.01~ N 7.03%
Each of the other compounds of the present invention listed in the Table above can be prepared in a manner analogous to that described in any one of Examples 1 to 3 Ex m le 4 In a series of tests carried out in a greenhouse the compounds of the present invention listed in the Table below were each sprayed at a rate of application of 5 kg of active substance per hectare, suspended in 500 litres of water per hectare, onto the soil before the sowing of _olium and Setaria and worked into the soil. Three weeks after the treatment the results thereof were evaluated, the results being expressed by a numerical scale extendiny from 0 to 4, the value 0 representing ..
no action and the value 4 representing destruction of the plant.
Compound of the present invention Lolium Setaria 1,3,3-Trimethyl-6-azabicyclo-(3,2,1)-octane-6-thiocarboxylic acid S--e-thyl . -.
ester ~ 4 1,3,3-Trimetilyl-6-- azabicyclo-¦3,2,1)-octane-6-thiocarbo~yllc acid S-methyl ester 4 1,3,3-Trimethyl-6--azahicyclo-(3,2,1)-octane-6-t]liocarboxylic acid S-propyl ester 4 ~G10~3~
Compoulld of the i nv en-tion ~,o.lium Set_rla 1,3,3-Trimethyl-6- ~zabicyclo-(3,2,1)-octane-G-dithiocarboxylic acid (2-propenyl) ester 4 3 1,3,3-Trimethyl-6-azabicyclo-(3,2,1)-octane-6-thiocarboxylic acid S-benzyl ester 3 O = no action
4 = destruction of -the plant - = no tested.
The following compounds have an analogous action __ _ _. _. _ _ _ .. . _ , ............. _ _ , '~ 1,3,3-Trir.letihy:L-G-azabicyclo-(3,2,1)-octane-i',-carboxylic acid me',;~y:L ester 1,3,3-Trimethyl-6-azabicyclo-(3,2,1)-octane-6-carboxylic acid ethyl ester lr3r3-Trimetilyl-6-azabicyclo-(3~2~l)-octane-6-carboxylic acid propyl ester l/3/3-Trimethyl-6-azabicyclo-(3/2/l)-octane-6-carboxylic acid butyl ester 1,3,3-Trimethyl-6-azabicyclo-(3,2,1)-octane-6-carboxylic acid isopropyl ester r3r3-Trimethyl-6-azabicyclo-(3r2r]-)-octane-6-carboxylic acid (2-propenyl)ester 1,3,3-Trimethyl 6-azabicyclo-(3,2,1)-octane-6-carboxy]ic acid phenyl ester 1,3,3-Trimethyl-6--aza~icyclo-(3,2,1)-octane-6-thiocarboxylic acid S-(4-fluorophenyl) ester 1,3,3-Trimethyl-6-azabicyclo-(3,2,1)-octane--6-carboxylic acid benzyl ester 1,3,3-Trimethyl-6-azabicyclo-(3,2,1)-octane-6-carboxylic acid pentyl ester ~ - 17 -3~3 E,~AMPL~ 5 In a series of tests carried out in a greenhouse the plants listed in the following Table were treated before their emergence with the listed agents being tested at a rate of application of 3 kg of active substance per hectare. For this purpose ti~e agents were in each case applied uniformly in the form of an aqueous dispersion using 500 li~res per hectare, onto the soil and then incorporated into the soil. The results three weeks after the treatment show that the compound of -the present invention was a better herbicidal agent tllan the agent used for O cor,lparison.
- 17a.--, ~ . , , ,, ~ .
3~
The results are expressed by a numerical scale extending from 0 to 10, the value 0 representing to-tal destruction of the plant and the value 10 representing no damage.
~ 18 ~
r~ u) r~_ ~Q ~ n ~ r~
- ~ rD n rD r~ r~ ~ 3 O rt O r~ ~ tD pl ~ ~
Il 1I rD n ~ 1- o r~ ~ ~s ~ o p) pl ~ ~h ~ rb I
rt rl )t ~ ~h I
- O O tD~ In ~-- o G~ ~ ~
~ ~ ~ ~ O
~ 1-- n ~ ~~J n ~ rD I h Ort IO r~ O IJ ~t rD ~:~ O ~ O ~ t1 tD r~rD ~ n ~ .
rD rn ~; x~: c P~ rD
rt o ~ o 1~ 1 rD(T rn o I ~s n r~~ rD o x P) rD
~t ,_` ~ ~ ~ N r:nD
O 1~ I' rDGO ~ n 1. tt ~ ~ r~
rD ~ < 1, c~ rD n n o~ rn ~ Q- O rD
td I ~ .
p) tl7--` It r~ I
rD rD ~ O
~ r~
It I
w w 3 kg/ha of active substance o o o Cotton - ~ ~ Soya bean o w o Rice o o o o o o Triticum Il IJ
o o o Hordeum o o o Avena o O o Alopecurus o o o Ech.inochloa o w O Setaria o w o Di~itaria ~-o o o Poa ''` ~ '' ." ' ' '~: ' .
l9 - : :
. .
The following compounds have an analogous action __ _ _. _. _ _ _ .. . _ , ............. _ _ , '~ 1,3,3-Trir.letihy:L-G-azabicyclo-(3,2,1)-octane-i',-carboxylic acid me',;~y:L ester 1,3,3-Trimethyl-6-azabicyclo-(3,2,1)-octane-6-carboxylic acid ethyl ester lr3r3-Trimetilyl-6-azabicyclo-(3~2~l)-octane-6-carboxylic acid propyl ester l/3/3-Trimethyl-6-azabicyclo-(3/2/l)-octane-6-carboxylic acid butyl ester 1,3,3-Trimethyl-6-azabicyclo-(3,2,1)-octane-6-carboxylic acid isopropyl ester r3r3-Trimethyl-6-azabicyclo-(3r2r]-)-octane-6-carboxylic acid (2-propenyl)ester 1,3,3-Trimethyl 6-azabicyclo-(3,2,1)-octane-6-carboxy]ic acid phenyl ester 1,3,3-Trimethyl-6--aza~icyclo-(3,2,1)-octane-6-thiocarboxylic acid S-(4-fluorophenyl) ester 1,3,3-Trimethyl-6-azabicyclo-(3,2,1)-octane--6-carboxylic acid benzyl ester 1,3,3-Trimethyl-6-azabicyclo-(3,2,1)-octane-6-carboxylic acid pentyl ester ~ - 17 -3~3 E,~AMPL~ 5 In a series of tests carried out in a greenhouse the plants listed in the following Table were treated before their emergence with the listed agents being tested at a rate of application of 3 kg of active substance per hectare. For this purpose ti~e agents were in each case applied uniformly in the form of an aqueous dispersion using 500 li~res per hectare, onto the soil and then incorporated into the soil. The results three weeks after the treatment show that the compound of -the present invention was a better herbicidal agent tllan the agent used for O cor,lparison.
- 17a.--, ~ . , , ,, ~ .
3~
The results are expressed by a numerical scale extending from 0 to 10, the value 0 representing to-tal destruction of the plant and the value 10 representing no damage.
~ 18 ~
r~ u) r~_ ~Q ~ n ~ r~
- ~ rD n rD r~ r~ ~ 3 O rt O r~ ~ tD pl ~ ~
Il 1I rD n ~ 1- o r~ ~ ~s ~ o p) pl ~ ~h ~ rb I
rt rl )t ~ ~h I
- O O tD~ In ~-- o G~ ~ ~
~ ~ ~ ~ O
~ 1-- n ~ ~~J n ~ rD I h Ort IO r~ O IJ ~t rD ~:~ O ~ O ~ t1 tD r~rD ~ n ~ .
rD rn ~; x~: c P~ rD
rt o ~ o 1~ 1 rD(T rn o I ~s n r~~ rD o x P) rD
~t ,_` ~ ~ ~ N r:nD
O 1~ I' rDGO ~ n 1. tt ~ ~ r~
rD ~ < 1, c~ rD n n o~ rn ~ Q- O rD
td I ~ .
p) tl7--` It r~ I
rD rD ~ O
~ r~
It I
w w 3 kg/ha of active substance o o o Cotton - ~ ~ Soya bean o w o Rice o o o o o o Triticum Il IJ
o o o Hordeum o o o Avena o O o Alopecurus o o o Ech.inochloa o w O Setaria o w o Di~itaria ~-o o o Poa ''` ~ '' ." ' ' '~: ' .
l9 - : :
. .
Claims (38)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A compound of the general formula I
(I), in which R represents a radical selected from an alkyl containing 1 to 7 carbon atoms; an alkenyl containing 2 to 7 carbon atoms;
a phenyl which may be substituted with chlorine; and a phenyl alkyl wherein the alkyl group contains 1 to 4 carbon atoms and wherein the phenyl group may be substituted with chlorine, and X and Y each represents an oxygen atom or a sulphur atom.
(I), in which R represents a radical selected from an alkyl containing 1 to 7 carbon atoms; an alkenyl containing 2 to 7 carbon atoms;
a phenyl which may be substituted with chlorine; and a phenyl alkyl wherein the alkyl group contains 1 to 4 carbon atoms and wherein the phenyl group may be substituted with chlorine, and X and Y each represents an oxygen atom or a sulphur atom.
2. A compound as claimed in claim 1, wherein R rep-resents a methyl, ethyl, n-propyl, isopropyl, allyl, butyl, sec.-butyl, isobutyl, tert.-butyl, butenyl, pentyl, isopentyl, benzyl, 4-chlorobenzyl, 2,4-dichlorobenzyl, phenyl or 4-chloro-phenyl group.
3. A compound as claimed in claim 1, which is 1,3,3-trimethyl-6-azabicyclo-(3,2,1)-octane-6-dithiocarboxylic acid S-ethyl ester.
4. A compound as claimed in claim 1, which is 1,3,3-trimethyl-6-azabicyclo-(3,2,1)-octane-6-dithiocarboxylic acid (2-propenyl) ester.
5. A compound as claimed in claim 1, which is 1,3,3-trimethyl-6-azabicyclo-(3,2,1)-octane-6-thiocarboxylic acid S-methyl ester.
6. A compound as claimed in claim 1, which is 1,3,3-trimethyl-6-azabicyclo-(3,2,1)-octane-6-thiocarboxylic acid S-propyl ester.
7. A compound as claimed in claim 1, which is 1,3,3-trimethyl-6-azabicyclo-(3,2,1)-octane-6-thiocarboxylic acid S-benzyl ester.
8. A compound as claimed in claim 1, which is 1,3,3-trimethyl-6-azabicyclo-(3,2,1)-octane-6-carboxylic acid methyl ester.
9. A compound as claimed in claim 1, which is 1,3,3-trimethyl-6-azabicyclo-(3,2,1)-octane-6-carboxylic acid ethyl ester.
10. A compound as claimed in claim 1, which is 1,3,3-trimethyl-6-azabicyclo-(3,2,1)-octane-6-carboxylic acid propyl ester.
11. A compound as claimed in claim 1, which is 1,3,3-trimethyl-6-azabicyclo-(3,2,1)-octane-6-carboxylic acid butyl ester.
12. A compound as claimed in claim 1, which is 1,3,3-trimethyl-6-azabicyclo-(3,2,1)-octane-6-carboxylic acid isopropyl ester.
13. A compound as claimed in claim 1, which is 1,3,3-trimethyl-6-azabicyclo-(3,2,1)-octane-6-carboxylic acid (2-prop-enyl) ester.
14. A compound as claimed in claim 1, which is 1,3,3-trimethyl-6-azabicyclo-(3,2,1)-octane-6-carboxylic acid phenyl ester.
15. A compound as claimed in claim 1, which is 1,3,3-trimethyl-6-azabicyclo-(3,2,1)-octane-6-thiocarboxylic acid S-(4-fluorophenyl) ester.
16. A compound as claimed in claim 1, which is 1,3,3-trimethyl-6-azabicyclo-(3,2,1)-octane-6-carboxylic acid benzyl ester.
17. A compound as claimed in claim 1, which is 1,3,3-trimethyl-6-azabicyclo-(3,2,1)-octane-6-carboxylic acid pentyl ester.
18. A process for the manufacture of a compound of the general formula I given in claim 1, in which R, X and Y have the meanings given in claim 1, wherein 1,3,3-trimethyl-6-azabi-cyclo-(3,2,1)-octane of the formula (a) is reacted with a halogeno-formic acid ester of the general formula in which R, X and Y have the meanings given above and Hal represents a halogen atom, or (b) is reacted in the presence of a base with a compound of the general formula X=C=Y , in which X and Y have the meanings given above, to form a salt of such a base of the general formula , in which X and Y have the meanings given above and B represents a cation derived from the base, and the salt is treated with an alkylating agent of the general formula R-Z, in which R has the meaning given above and Z represents a halogen atom, an alkyl sulphuric acid group or a toluene sulphonic acid group, or (c) is reacted with a phosgene compound of the general formula Hal2C=X
in which X and Hal have the meanings given above, to form a 1,3,3-trimethyl-6-azabicyclo-(3,2,1)-octane-6-carboxylic acid halide of the general formula in which X and Hal have the meanings given above, which is then reacted with an oxygen- or thio-compound of the general formula R-Y(-)B(+) in which R and Y have the meanings given above and B(+) represents a cation, or (d) a 1,3,3-trimethyl-6-azabicyclo-(3,2,1)-octane-6-carboxylic acid halide of the general formula in which X has the meaning given above and Hal represents a halo-gen atom, is reacted with an oxygen- or thio-compound of the general formula R-Y(-)B(+) in which R and Y have the meanings given above and B(+) represents a cation.
in which X and Hal have the meanings given above, to form a 1,3,3-trimethyl-6-azabicyclo-(3,2,1)-octane-6-carboxylic acid halide of the general formula in which X and Hal have the meanings given above, which is then reacted with an oxygen- or thio-compound of the general formula R-Y(-)B(+) in which R and Y have the meanings given above and B(+) represents a cation, or (d) a 1,3,3-trimethyl-6-azabicyclo-(3,2,1)-octane-6-carboxylic acid halide of the general formula in which X has the meaning given above and Hal represents a halo-gen atom, is reacted with an oxygen- or thio-compound of the general formula R-Y(-)B(+) in which R and Y have the meanings given above and B(+) represents a cation.
19. A process as claimed in claim 18, wherein the 1,3,3-trimethyl-6-azabicyclo-(3,2,1)-octane is dissolved in a solvent.
20. A process as claimed in claim 18 or 19, wherein the reaction with the halo-formic acid ester is carried out in the presence of an acid-binding agent.
21. A process for the manufacture of a compound of the general formula I given in claim 1, in which R, X and Y have the meanings given in claim 1, wherein a 1,3,3,-trimethyl-6-azabicyclo-(3,2,1)-octane-6-carboxylic acid halide of the general formula in which X has the meaning given above and Hal represents a halogen atom, is reacted with an oxygen- or thio-compound of the general formula R-Y(-)B(+) in which R and Y have the meanings given above and B(+) represents a cation.
22. A method of protecting a living plant against weeds, wherein the area in the vicinity of the living plant is treated with a compound as claimed in claim 1, 2 or 3.
23. A method of protecting a living plant against weeds, wherein the area in the vicinity of the living plant is treated with a compound as claimed in claim 4, 5 or 6.
24. A method of protecting a living plant against weeds, wherein the area in the vicinity of the living plant is treated with a compound as claimed in claim 7, 8 or 9.
25. A method of protecting a living plant against weeds, wherein the area in the vicinity of the living plant is treated with a compound as claimed in claim 10, 11 or 12.
26. A method of protecting a living plant against weeds, wherein the area in the vicinity of the living plant is treated with a compound as claimed in claim 13, 14 or 15.
27. A method of protecting a living plant against weeds, wherein the area in the vicinity of the living plant is treated with a compound as claimed in claim 16 or 17.
28. A method of protecting a living plant against weeds, wherein the area in the vicinity of the living plant is treated with a compound as claimed in claim 1, 2 or 3, and wherein a single compound of the general formula I is used for the treatment in an amount within the range of from 1 to 8 kg of hectare.
29. A method of protecting a living plant against weeds, wherein the area in the vicinity of the living plant is treated with a compound as claimed in claim 1, 2 or 3, and wherein two or more compounds of the general formula I are used for the treatment in a total amount within the range of from 1 to 8 kg per hectare.
30. A method of protecting a crop area against weeds, wherein the crop area is treated with a compound as claimed in claim 1, 2 or 3.
31. A method of protecting a crop area against weeds, wherein the crop area is treated with a compound as claimed in claim 4, 5 or 6.
32. A method of protecting a crop area against weeds, wherein the crop area is treated with a compound as claimed in claim 7, 8 or 9.
33. A method of protecting a crop area against weeds, wherein the crop area is treated with a compound as claimed in claim 10, 11 or 12.
34. A method of protecting a crop area against weeds, wherein the crop area is treated with a compound as claimed in claim 13, 14 or 15.
35. A method of protecting a crop area against weeds, wherein the crop area is treated with a compound as claimed in claim 16 or 17.
36. A method of protecting a crop area against weeds, wherein the crop area is treated with a compound as claimed in claim 1, 2 or 3, and wherein a single compound of the general formula I is used for the treatment in an amount within the range of from 1 to 8 kg per hectare.
37. A method of protecting a crop area against weeds, wherein the crop area is treated with a compound as claimed in claim 1, 2 or 3, and wherein two or more compounds of the general formula are used for the treatment in a total amount within the range of from 1 to 8 kg per hectare.
38. A method of protecting a crop area against weeds, wherein the crop area is treated with a compound as claimed in claim 1, 2 or 3, and wherein the crop is a cauliflower, beetroot, tomato, bush bean, soya bean, cotton or rice crop.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19762632915 DE2632915A1 (en) | 1976-07-19 | 1976-07-19 | 1,3,3-TRIMETHYL-6-AZABICYCLO- (3.2.1) -OCTAN-6-CARBONIC ACID ESTER, METHOD FOR THE PRODUCTION OF THESE COMPOUNDS AND THE HERBICIDES CONTAINING THEM |
| DEP2632915.7 | 1976-07-19 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1100138A true CA1100138A (en) | 1981-04-28 |
Family
ID=5983626
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA282,400A Expired CA1100138A (en) | 1976-07-19 | 1977-07-11 | Herbicidally active 1,3,3-trimethyl-6-azabicyclo-(3,2, 1)-octane-6-carboxylic acid esters and their manufacture and use |
Country Status (34)
| Country | Link |
|---|---|
| JP (1) | JPS5312855A (en) |
| AR (1) | AR216084A1 (en) |
| AT (1) | AT355861B (en) |
| AU (1) | AU511783B2 (en) |
| BE (1) | BE856933A (en) |
| BG (2) | BG27027A3 (en) |
| BR (1) | BR7704733A (en) |
| CA (1) | CA1100138A (en) |
| CH (1) | CH627920A5 (en) |
| CS (1) | CS192582B2 (en) |
| DD (1) | DD131070A5 (en) |
| DE (1) | DE2632915A1 (en) |
| DK (1) | DK324977A (en) |
| ES (1) | ES460737A1 (en) |
| FI (1) | FI772095A (en) |
| FR (1) | FR2359142A1 (en) |
| GB (1) | GB1588934A (en) |
| GR (1) | GR71649B (en) |
| HU (1) | HU178752B (en) |
| IE (1) | IE45359B1 (en) |
| IL (1) | IL52455A (en) |
| IT (1) | IT1113599B (en) |
| LU (1) | LU77781A1 (en) |
| MX (1) | MX4852E (en) |
| NL (1) | NL7707038A (en) |
| NO (1) | NO147603C (en) |
| PL (1) | PL103690B1 (en) |
| PT (1) | PT66822B (en) |
| RO (1) | RO71241A (en) |
| SE (1) | SE424868B (en) |
| SU (1) | SU656464A3 (en) |
| TR (1) | TR19833A (en) |
| YU (1) | YU164477A (en) |
| ZA (1) | ZA774346B (en) |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES303195A1 (en) * | 1963-08-19 | 1965-03-16 | Ciba Geigy | Procedure for the obtaining of N- (n, N-bicicloalquilenoimino) -ditiocarbonic acids. (Machine-translation by Google Translate, not legally binding) |
| US3705165A (en) * | 1970-08-05 | 1972-12-05 | Elmar Sturm | N-carbonyl derivatives of azabicyclooctanes |
| US3820974A (en) * | 1970-08-05 | 1974-06-28 | Ciba Geigy Corp | Control of weeds with n carbenyl derivatives of azabicyclooctanes |
-
1976
- 1976-07-19 DE DE19762632915 patent/DE2632915A1/en not_active Withdrawn
-
1977
- 1977-06-24 NL NL7707038A patent/NL7707038A/en unknown
- 1977-07-01 YU YU01644/77A patent/YU164477A/en unknown
- 1977-07-04 CS CS774434A patent/CS192582B2/en unknown
- 1977-07-04 MX MX77100800U patent/MX4852E/en unknown
- 1977-07-05 FI FI772095A patent/FI772095A/fi not_active Application Discontinuation
- 1977-07-05 IL IL52455A patent/IL52455A/en unknown
- 1977-07-07 TR TR19833A patent/TR19833A/en unknown
- 1977-07-11 CA CA282,400A patent/CA1100138A/en not_active Expired
- 1977-07-14 AU AU27008/77A patent/AU511783B2/en not_active Expired
- 1977-07-14 ES ES460737A patent/ES460737A1/en not_active Expired
- 1977-07-15 BG BG7736916A patent/BG27027A3/en unknown
- 1977-07-15 BG BG7736916D patent/BG28027A3/xx unknown
- 1977-07-15 IE IE1472/77A patent/IE45359B1/en unknown
- 1977-07-15 DD DD7700200094A patent/DD131070A5/en unknown
- 1977-07-15 LU LU77781A patent/LU77781A1/xx unknown
- 1977-07-15 CH CH880877A patent/CH627920A5/en not_active IP Right Cessation
- 1977-07-16 PL PL1977199694A patent/PL103690B1/en unknown
- 1977-07-18 HU HU77SCHE615A patent/HU178752B/en unknown
- 1977-07-18 AR AR268467A patent/AR216084A1/en active
- 1977-07-18 PT PT66822A patent/PT66822B/en unknown
- 1977-07-18 NO NO772552A patent/NO147603C/en unknown
- 1977-07-18 SE SE7708277A patent/SE424868B/en unknown
- 1977-07-18 RO RO7791078A patent/RO71241A/en unknown
- 1977-07-18 FR FR7721934A patent/FR2359142A1/en active Granted
- 1977-07-18 DK DK324977A patent/DK324977A/en not_active Application Discontinuation
- 1977-07-18 GR GR53987A patent/GR71649B/el unknown
- 1977-07-18 AT AT517477A patent/AT355861B/en not_active IP Right Cessation
- 1977-07-18 BR BR7704733A patent/BR7704733A/en unknown
- 1977-07-19 ZA ZA00774346A patent/ZA774346B/en unknown
- 1977-07-19 BE BE179455A patent/BE856933A/en not_active IP Right Cessation
- 1977-07-19 IT IT25888/77A patent/IT1113599B/en active
- 1977-07-19 JP JP8657277A patent/JPS5312855A/en active Granted
- 1977-07-19 GB GB30241/77A patent/GB1588934A/en not_active Expired
- 1977-07-19 SU SU772504515A patent/SU656464A3/en active
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |