HERBICIDALLY ACTIVE 1,3,3-TRIMETHYL-6-AZABICYCLO-(3,2, 1)-OCTANE-6-CARBOXYLIC ACID ESTERS AND THEIR MANUFACTURE AND USE

TRADUCTION NON-DISPONIBLE

English 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
<IMG> (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.

Claims

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A compound of the general formula I
<IMG> (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.
21

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
<IMG>
(a) is reacted with a halogeno-formic acid ester of the general
formula
<IMG>
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
<IMG> ,
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
22

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
<IMG>
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
<IMG>
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(+)
23

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
<IMG>

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.
26

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.
27

Description

38
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),
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
.
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,
.
-- 4

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
.
..

313
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 -

38
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
- 14 -
.: :
..

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
- 15 -
. ",;
.

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
- 16 -

~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 ~

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