Note: Descriptions are shown in the official language in which they were submitted.
77~
This is a division of the Canadian p~ten-t
application n 331.488 filed on July 10th, 1979.
The present invention relates to herbicidal
agents containing, as herbicidal active ingredients,
substituted acetanilides and, as antagonistic agents,
tetrahydro-1,3-oxazines. The invention also relates to a
process for selectively combating unwanted plant growth
with these herbicidal agents.
Substituted acetanilides of the formula
R2 ~ \ Co-C~ -X I,
where R denotes hydrogen, linear or branched alkyl or
alkoxy of up to 5 carbon atoms, Rl denotes hydrogen, halogen,
or linear or branched alkyl or alkoxy of up to 5 carbon
atoms, R2 denotes hydrogen, halogen, or linear or branched
alkyl or alkoxy of up to 5 carbon atoms, R together with
R2 denotes an alkylene chain of up to 6 carbon atoms which
is linked in the o-position and may be substituted by
linear or branched alkyl of up to 4 carbon atoms, X denotes
chlorine or bromine, and A denotes azole which is attached
via a ring nitrogen atom and may be mono ox polysubstituted
by halogen, phenyl, alkyl, alkoxy, alkylthio or per-
fluoroalkyl, each of up to 4 carbon atoms, cyano, carboxy,
carbalkoxy of up to 4 carbon atoms in t~le alkoxy, or
alkanoyl of up to 4 carbon atoms, or ~ denotes salts of
azoles containing 2 or 3 nitrogen atoms, have an excellent
her~icidal action, but cause damage to crops such as
Indian corn and Gramineae.
Therefore, it becomes necessary to add
antagonistic agents to offset this poor tolerance of
herbicidal acetanilides by certain crop plants. ~.
'7~
Herbicidal agents containing, in addition to
chloroacetanilides as herbicidal active ingredients,
antagonistic compounds have been disclosed in the United States
patent n 3,719,466 and German Laid~Open Applications
DE_OS nos 2,218,097 and 2,402,983.
United States patent n 3,719,~66 teaches
that damage to sorghum and wheat caused by the herbiciae
2~chloro-2',6'-diethyl-N-(methoxymethyl)~acetanilide can be
avoided by treating the seed with an antagonistic agent such
as N,N-diallylacetamide.
German Laid-Open Application DE-OS
n 2,218,097 mentions combinations of the same ac-tive ingredient
and other herbicidal acetanilides with antagonistic amides,
e.g., N,N diallyldichloroacetamide. However, these amides are
preferably used as antidotes for herbicidal thiolcarbamates.
German ~aid-Open Application DE-OS n 2,~02,983
relates to herbicidal agents containing dichloroacetamides
known from German Laid-Open Application DE-OS n 2,218,097, or
dichloroacetamides s-tructurally simi.lar to them, and chloro~
acetanilides oE a dif~erent constitution, especially
N-(2'-methoxyethyl)-2,6-dimethylchloroacetanilide. These
agents are suitable merely for selective weed control in
Indian corn. Also said to be suitable as antagonistic
compounds are, inter alia, dichloroacetamides in which both
substituents on the nitrogen atom ~orm, with it, a 6-membered
heterocycle containing a further hetero atom and which is
unsubstituted or mono- or polysubstituted by lower alkyl.
However the only representative of this group which is
mentioned is N-dichloroacetylmorpholine.
The invention relates to herbicidal agents
containing at least one substituted acetanilide of the formula I
-- 2 --
~4g~
/ CH2 -A
~ N I,
,' ~ _// CO-C112-X
R2 R
where R denotes hydrogen, linear or branched alkyl or
alkoxy of up to 5 carbon atoms, R denotes hydrogen, halogen,
or linear or branched alkyl or alkoxy of up to 5 carbon
atoms, R denotes hydrogen, halogen, or linear or branched
alkyl or alkoxy of up to 5 carbon atoms, R together with
R denotes an alkylene chain of up to 6 carbon atoms which
is linked in -the o-position and may be substi-tuted by
linear or branched alkyl of up to 4 arbon atoms, X denotes
I chlorine or bromine, and A denotes azole which i5 attached
- via a ring nitrogen atom and may be mono-or polysubstituted
by halogen, phenyl, alkyl, alkoxy, alkylthio or per-
fluoroalkyl, each of up to 4 carbon atoms, cyano, carboxy,
20 carbalkoxy of up to carbon atoms in the alkoxy, or alkanoyl
of up to 4 carbon atoms, or A denotes salts of azoles
containing 2 or 3 ni-trogen atoms; and at least one tetrahydro-
1,3-oxazine of the formula II . .
R \ ~ 11
4 / l ~-CO-R
R ~ ~7
R R6
-- 3
77~
where R clenotes linear or branched haloalkyl of up to 3
carbon atoms, R , R , R , R and R are identical or different
and each denotes hydrogen or linear or branched alkyl oE up
to 3 carbon atoms, R6 denotes hydrogen or linear or branched
alkyl of up -to 8 carbon atoms, R7 denotes hydrogen~ linear
or branched alkyl of up to ~ carbon atoms, alkoxyalkyl of
up to 6 carbon atoms or dialkoxyalkyl of up to 8 carbon atoms,
and R6 and R7 may together form a methylene chain of 4 o~ 5
carbon atoms;may be used both in Indian corn and in cereal
crops. These tetrahydro-1,3-oxazines are excellently suited
for increasing the tolerance of crop plants to herbicidal
substituted acetanilides oE the formula I. The good
herbicidal action of the acetanilides is retained and damage
to the crop plants is prevented.
Acetanilides w~ose tolerance by crop plants
can be increased by the -tetrahydro-1,3-oxazines are those
of the formula I in which R is hydrogen, alkyl of a maximum
oE 5 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl,
n-butyl, sec-butyl, i.sobu-tyl, tert-butyl, linear and
branched pentyl, and alkoxy o:E a maximum oE 5 carbon atoms,
I such as methoxy, ethoxy, propoxy, butoxy and pentoxy;
Rl and R are hydrogen, halogen, such as
fluorine, chlorine, bromine and iodine, alkyl of a maximum
of 5 carbon atoms, such as methyl, ethyl, p-propyl,
isopropyl, p-butyl, sec-butyl, isobutyl, tert-butyl, linear
and branched pentyl, a~d alkoxy of a maximum of 5 carbon
atoms, such as methoxy, ethoxy, propoxy, butoxy, and
pentoxy;
.
7(:)
R2 together with R is an alkylene chain of a maximum Or
6 carbon atom~, linked in the o-po~ition and unsub3tituted or
sub3tituted by alkyl Or a maximum of 4 carbon atom~, e.g.,
ethyleneg trimethylene, tetramethylene, 1-methyltri~ethylene,
1,1-dimethyltrimethylene, and 1,1-dimethyltetramethylene,
X is chlorine, bromine or iodine, preferably chlorine;
A i~ an azole attached via a ring nitrogen atom, e.g.,
pyrrole, pyrazole, imidazole, 1,2,4-triazole, 1,2,3-triazole,
and tetrazole, which be mono- or polysubstituted by halogen,
phenyl, alkyl, alkoxy, alkylthio or perfluoroalkyl, each of
up to 4 carbon atoms, cyano, carboxy, or carbalkoxy with up
to 4 carbon atoms in the alkoxy, or alkanoyl Or up to 4 carbon
atoms, the sub~tituents being identical or dif~erent, ~uch a~
2,6~dimethylpyrrole, tetramethylpyrrole, 3(5)-methylpyrazole,
4-methylpyrazole, ~(5)-ethylpyrazole, 4-ethylpyrazole, 3(5)-i~o-
propylpyrazole, 4-isopropylpyrazole, 3,5-dimethylpyrazole,
3,5-dimethyl-4-acetylpyrazole, 3,5-dimethyl-4-propionylpyrazole,
3,4,5-trimethylpyr~zole, 3(5)-phenylpyrazole, 4-phenylpyrazole,
3,5-diphenylpyrazole, 3(5)-phenyl-5(3)-methylpyrazole, 3(5)-
2C -chloropyrazole, 4-chloropyrazole, 4-bromopyrazole, 4-iodo-
pyrazole, 3,4,5-tribromopyrazole~ 3,5-dimethyl-4-chloropyrazole,
3~5-dimethyl-4-bromopyrazole, 4-chloro-3(5)-methylpyrazole,
4-bromo 3(5)~methylpyrazole, 4-methyl-3,5-dichloropyrazole,
3(5 }methyl-4,5(3)-dichloropyrazole~ 3(5)-chloro-5(3)-methyl-
pyrazole~ 4-methoxypyrazole, 3(5)-methyl-5(3)-methoxypyrazole,
3(5)-ethoxy-4,5(3)-dimethylpyrazole, ~(5)-methyl-5(3)~trifluoro-
methylpyraæole, 3,5-bi~-tri~luoromethylpyrazole, 3(5~methyl-
D5 ( 3)-carbethoxypyrazole, 3~5 bis-carbethoxypyrazole, 3,4,5-tri~-
carbethoxypyrazole, 3(5)-methyl-5~3)-methylthio-4-carbethoxypyrazole,
`." -` 1~4~
.. .
4-methyl-3,5-biscarbethoxypyrazole, 4-cyanopyrazole, 4-methoxy-
-3,5-dichloropyrazole, 4,5-dichloroimidazoleg 2-ethyl-4,5-di-
chloroimidazole, 2-methyl-4,5-dichloroimidazole, 3(5)-methyl-
-1,2,4-triazole, 3,5-dimethyl-1,2,4--triazole, 3(5)-chloro-1,2,4-
-triazole, 3(5)-bromo-1,2,4-triazole, 3(5)-chloro-5(3)-methyl-
-1,2,4-triazole, 3,5~dichloro-1,2,4-triazole, 3,5-dibromo-1,2,ll-
trlazole, 3(5)-chloro-5(3)-cyano-1,2,4-triazole, 3(5)-chloro-5(3)-
-phenyl-1,2,4-triazole, 3(5)-chloro-5t3)-carbomethoxy-1~2,4-tri-
azole, 3(5) methylthio-1,2,4-triazole, 4(5)-methyl-1,2,3-tri-
azole, 4,5-dimethyl-1,2,3-triazole, 4(5)-phenyl-1,2,3-triazole,
4(5)-chloro-1,2,~-triazole, 1,2,3-triazol-4(5)-yl-carboxylic
acid ethyl ester, 1,2,3-triazol-4,5-yl-dicarboxylic acid di-
methyl ester, 5-methyltetrazole, 5-chlorotetrazole, and tetra-
zolyl-5-carboxylic acid ethyl ester.
Furthermore, the radical A may, when the optionally sub~
stituted azole contains 2 or 3 nitrogen atoms, also be attached
in a saltlike manner to one of the usual strong inorganic or
organic acids, e.g., hydrochloric acid, hydrobromic acid, nitric
acid, sulfuric acid, tetrafluoboric acid, fluo~ul~onic acid~ and
2C formic acid, a halogenated carboxylic acid, e.g., trichloroac~tic
acid, an alkanesulronic acid, e.~., methanesulfonic acid, a
halogenated alkanesulfonic acid, e.g., trifluoromethanesulfonic
acid and perfluorohexanesu~fonic acid, and an arylsulfonic acid,
e.g. dodecylbenzenesulfonic acid.
Preferred acetanilides are those which bear methyl or
ethyl in the 2- and 6-po3ition3 on the phenyl ring and hydrogen,
methyl or ethyl in the 3-position; suitable azoIes are pyrazole~
imidazole, triazole and tetrazole, which are unsubstituted or
~4L'7~0
sub~tituted by lower alkyl~ alkoxy, alkylthio, carbalkoxy,
cyano or halogen.
In particular, the herbicidal agents according to the
invention contain the following acetanilides:
2-chloro-2',6'-dimethyl-N-(pyrazol-1-yl-methyl)-acetanilide,
2-chloro-2'-methyl-6'-ethyl-N (pyrazol-1-yl-methyl)-acet-
anilide~ 2-chloro-2',6'-dimethyl-N-(4-methylpyrazol-1-yl-
methyl)-acetanilide, 2-chloro-2-methyl-6-ethyl-N-(4-methoxy-
pyraæol-1-yl-methyl)-acetanilide, 2-chloro-2'-methyl-6'-
ethyl-N-~3(5)-methylpyrazol-1-yl)-acetanilide 3 2-chloro-2'~
6t-dimethyl-N-(3,5-dimethylpyrazol-1-yl-methyl)-acetanilide,
2-chloro-2',6'-dimethyl-N-(1,2,4-triazol-1-yl-methyl)-acet-
anilide, 2-chloro-2',6'-dimethyl-N-(4-chloropyrazol-1-yl-
-methyl)-acetanilide, 2-chloro-2',3'~6' trimethyl-N-(pyrazol-
-1-yl-methyl)-acetanilide, 2-chloro-2'-methyl-6~-ethyl-N (3,5-
-dimethylpyrazol-1 yl-methyl)-acetanilide, 2-chloro-21,6'-di-
ethyl-N-~3,5-dimethylpyrazol-1-yl-methyl)-acetanilide, 2-chloro-
2',3',6'-trimethyl-N-(3,5-dimethylpyrazol-1-yl-methyl)-acet-.
anilide, 2-chloro-2',6'-diethyl-N-(4-methylpyraæol-1-yl-m~thyl)-
2C -acetanilide, 2-chloro-2'-methyl-6'-ethyl-N-(4-methylpyrazol-
-1-ylmethyl)-acetanilide, 2-chloro-2',3',6'-trimethyl-N-(4-me-
thylpyrazol-l~yl-methyl)-~cetanilide 3 2-chloro-2' 6'-dimethyl-
-N-(3 (5)-methylpyrazol-1-yl-methyl)-acetanilide, 2-chloro~
-2~,6~-diethyl-N-(3-(5)-methylpyrazol-1-yl-methyl) acetanilide,
2-chloro 2',6'-dimethyl-N-(4-methoxypyrazol-1-yl-methyl)-acet~
anilide, 2-chloro-2',6'-diethyl~N-(pyrazol-1 yl-methylj-acet-
anilide, 2~chloro-2',6'-dimethyl~N-(4,5-dichloroimidazol-1-yl-
-methyl)-acetanilide~ 2-chloro~2' meShyl~6' ethyl-N~(4,5-di-
477C~
chloroimidazol~l~yl-methyl)-acetanilide~ 2 c~loro,2'~methyl-
-6'-ethyl-N-(2~ethyl-4,5-dichloroimidazol-1-yl~methyl)-acet-
anilide, 2-chloro-2',6'-diethyl-N ~4,5-dichloroimidazol l~yl-
-methyl)-acetanilide, 2-chloro-2'-methyl-6'-ethyl-~-(1,2,4-tri-
a~ol--1-yl-me-thyl)-acetanilide, 2-chloro-2',6'~diethyl-N-(1,2,4-
-triazol-l-yl~methyl)~ace-tanilide and 2~chloro-2',3',6'-tri-
methyl-N-(1,2,4-triazol-1-yl-methyl)-acetanillde.
The acetanilides of the formula I are disclosed in
Germain laid-Open Application published under DE-OS 2,648,008
and Canadian Patent Application n 312,376 filed on September
29, 1978. They may be obtained by reaction of 2-halo-N-halo-
methylacetanilides ~f the formula V with a lH-azole of the for-
mula H-A in accordance with the following equation:
R R
- N ~ 2 + H-A ~ ~ ~ / 2 A +
~ ~ ~ CO-CH2 X ,~ \~0-CH2-X
V
R, Rl, R2 and X have the above meanings and A denotes an azole
linked via a ring nitrogen atom and which may be mono- or poly-
substituted by halogen, phenyl, alkyl, alkoxy, alkylthio or
perfluoroalkyl, each of up to 4 carbon atoms in the alkoxy, or
alkanoyl of up to 4 carbon atoms.
Suitable antagonistic agents are tetrahydro-1,3 -
oxazines of the formula II in which the substituents Rl to R5
are identical or different and each denotes~hydrogen or alkyl
of up to 3 carbon atoms, especially hydrogen or methyl.
and R7
. ..
4~7~
denote hydrogen or alkyl of up to 8 carbon atom~, such a~
methyl, ethyl, n-yropyl, isopropyl, butyl, hexyl, heptyl
and octyl.
R may also denote alkoxyalkyl o~ up to 6 carbon atoms
or dialkoxyalkyl of up to 8 carbon atoms, e.g., methoxymethyl
and dimethoxymethyl. R and R7 may together form a methylene
chain o~ 4 or 5 carbon atomsO R denotes haloalkyl of up to
3 carbon atoms, preferably chloroalkyl3 and especially chloro-
methyl and dichloromethyl.
Preferred tetrahydro-1,3-oxazines are N-dichloroacetyl-4g4-
-dimethyltetrahydro-1,3-oxazine and N-dichloroacetyl-4,4,6-tri-
methyltetrahydro-1,3-oxa~ine,
These tetrahydro-1,3 - oxazines o~ the formula IX are
obtained by reaction of a compound of the formula
R2 ~,1
R4 ~ NH . . III,
R5 R6
where R1, R2~ R3, R4, R5, R6 and R7 have the above meanings,
with an acid chloride o~ the formula
2C R-CO-Cl IV,
where R has the above meanings9 in the presence of an agenk
which binds hydrogen chloride and in an inert solvent or diluent.
Examples o~.agent~ which bind hydrogen chloride are inorganic
bases~ such aq alkali metai carbonates, alkali metal bicarbonate3
and alkali metal hydroxides, and organic bases, e.g., tertiary
amine~, such a~ trialkylamines, and especially triethylamine~
Suitable inert solvents or diluents are hydrocarbon~, such
as toluene, xylene~ ligroin and cyclohexane 3 halogenated hydro-
7~
carbon~, such as dichloromethane, chloro~orm and carbon tetra-
chloride, and ethers, such a~ diethyl ether, diisopropyl ether,
tetrahydrofuran~ dioxane and ani~ole.
The following example illu~trates the production of the
tetrahydro-1,3-oxazines. Park~ by weight bear the s~ne
relationship to parts by volume as kilogram~ to liters.
EXAMPLE 1
At ~10 C and while stirring, 23.2 parts by weight of dichloro-
acetyl ehloride in 100 part~ by ~olume o~ toluene i~ dripped
into 23.0 part~ by weight of 4,4-dimethyltetrahydro-1,3~oxazine
and 20.7 part~ by weight of triethylamine in 100 parts by volume
of tolue~e. After the mixture has been stirred for 2 hours at
room temperature, there are added 150 parts by volume of
methylene chloride and enough water for 2 clear phases to be
formed. The organic phase is separated and washed twice, each
time with 50 part~ by ~olume of water. After drying and
evaporation o~ the solvents under reduced pressure, there is
isolated 41 parts by weight of N-dichloroacetyl-4,4-dimethyl-
tetrahydro~ oxazine o~ melting point 105-106C, which melts,
2C after recrystallization from methanol, at 106-107C~
a 13 2 2 2 MW: 226
calc.: C 42.5 H 5.8 N 6.19
found: C 42.6 H 5~8 N 6.2
The following compounds may be prepared analo~ously:
-- 10 --
'77~
3 R R
R4 ~ N-C0-R
'J~0 ~ R7
No. R R1 R2 R3 R4 R5 R6 R7 m.p./b.p./~
,
1 CH~Cl CH3 CH3 H H H H H b-p 0.067 mbar
90 C
2 CH2Cl CH3~ CH3 H H CH3 H H
3 CHCl2 CH3 CH3 . H H H H H m.p.: 108C
4 CHC12 CH3 CH3 H H H CH3 H oil
5 CHC12 CH3 CH3 H H H C2H5 H 1.5152
6 CHC12 CH3 CH3 H H Hn C3H7 H 1~5010
7 ~HCl2 CH3 CH3 H H H i C3H7 H
8 CHC12 CH3 CH3 H H H 3 3
2 3 3 H H CH3 C2H5
10 CHC12 CH3 CH3 H H H CH3 CH30CH2
11 -CHCl2 CH3 CH3 H H CH3 H H m.p.: 56C
12 CHCl2CH3CH3 H 3 3 H 1.4918
- 13 CHC12CH3CH3 H H CH3C2H5 H 1.4949
2C 14 CHC12CH3CH3 H H CH3n-C3H7 H 1.4915
15 CHC12CH3~H3 H H CH3 3 7 1.4945
16 CHC12H 3 3 H Hm.p.: 64C
17 CHC12H H CH~ CH3 H 3 m.p: 80C
la CHCl2 H H CH3 ~CH3 H - 2 5 H
19 CHC.12 H H CH3 CH3 H i-C3H7 H - m.p: 84C
CHCl2 H H CH3 CH3 CH3 H H
-- 11 ~
7~
.
No. R R1 R2R3 R4 R5 R6 R7 m,p./b,p /n25
. ~ .. ..... . . . _
21 CHCl2 H HCH3 CH3 CH3 3
22 CHC12 H HCH3 CH3 CH3C2H5 H
23 CHCl2 H HCH3 C~3 CH3i C3H7
24 CHGl2 H 3 H3 H H3 CH3
CHC12 H HCH3 CH3 H 3 3 2
26 CHC12 CH3 CH3H H CH3 CH-nC4H9 H 1.4849
C2H5
~7 CHC12 CH3 CH3H H CH3 CH3 CH3
28 CHC12 CH3 CH3H H CH3 CH3~ C2H5
29 CHC12 CH3 CH3H H CH3 H CH(OCH3)2 oil
CHC12 CH3 CH3H H CH3 CH3 CH30CH2 oil
31 CHC12 CH3 CH3H H CH3 ~ (C~l2)~i oil
32 CHC12 CH3 CH3H H CH3 (C~2)5 oil
33 CC13 CH3 CH3H H H H H m.p.: 103C
34 CC13 GH3 CH3H H CH3 H H
35 CH~-CH2Cl CH3 CH3 H H H H H
36 CH2-CH2Cl CH3 CH3 H H CH3 H H
Some of the starting materials of the formuIa III needed
the preparation of the tetrahydro- 1,3 _ oxazines are known
from Rec. trav. chim. P.B., 78, 315, 1959 and J. Org. Chem.,
38, 36, 1973. They may be ~repared by conventional methods,
(Tetrahedron, 309 3315, 1974; Rec. trav. chim. P.B., 78, 315,
1959? in accordance with the following eq~uation:
.
-- 12 -
; ~4~L770
2 1 7 3R2 R
R4 ~ NH2 ~ O=C ~R6 -H O ~ ~
R5 OH 2 R5~0 R
III
,
The ~ollowing example illustrate~ the preparation Or the
starting materials. Part~ by weight bear the same relation~hip
to part~ by volwne as kilo~rams to liters.
EXAMPLE 2
1,170 ~art3 by weight of 2-methyl-2 aminopentan-4-ol is
placed in a stirred flask. With external cooling, 440 part~ by
weight of acetaldehyde is run in over a period of about 40 minutes
at 15-20C. The reaction mixture is ~tirred for a further
- 15 minutes at 20C. After the addition of 600 parts by volume
of toluene, 182 parts by weight of water is separated off over
a period of 2 hours by azeotropic distillation. The reaction
product is subjected to fractional distillation. After removal
o~ the solvent there is obtained 1j3'12 parts by weight of
2~4,4,6-tetramethyltetrahydro-1,3-oxazine with a purity
2C (according to gas chromatography) of 98%,equivalent to a yield
of 94% of theory, based on 2-methyl-2-aminopentan-4 ol~
Boiling point (13 mbars): 53-54C.
nD: 1.4340.
The following compound~ of the formula III are prepared
in 'he same ~ay,
'
~ 13 -
.
7~1~
,R2
R3 ~ ~ ~H
Rl R2 ~3 R4 R5 R6 R7 n20 b.p,(mbars) Cc]
~ _ . ~ . .
CH3 CH3 H H H H H 1-4290 b.p.(l53) 87
3 3 H H H CH3 1.4372 b-p-(20) 42-43
3 3 H H HC2H5 1.4392 b-p-(2606) 9
; CH3 ~H3 H H H Hnc3H7 1-4371 b-p-(26.6) 9 7
lOCH3 CH3 H H H HiC3H7 1-4391 b-p-(26~6) 9
CH3 CH3 H H H H CH 4 9 1.4442 b.p.~0,27~ 54 55
C2H5
CH3 CH3 H H CH3 H H 1-4394 b~p-(13 3) 47-48
CH3 3 H H CH3 H CH3 1.434Q b.p.(13.3) 5
CH3 CH3 H H CH3 HC2H5 1.4345 b~p-(13.3)
3 3 H CH3 Hnc3H7 1-4380 b-P-(0.27)
CH3 CH3 H H CH3 -HiC3H7 1.4341 b-p~(13.3) 5
CH3 CH3 H H CH3 HC ~ C H 1.4451 b-p-(0.27) 5 55
2C CH3 CH3 H 3 2 5 1.4451 b.p.(20~ 59-60
CH3 CH3 H H CH3CH3 CH30~H2 1.4415 b-p-(26.6)
CH3 CH3 H H H- (CH2)4- 1.4689 b-p-(26.6) 97 98
3 3 3 ~(CH2)4 - 1-4651 b-p (o 2 ) 47-48
CH3 CH3 H H CH - (CH2)5 - 1-4690 b-p-(0.27)
H H CH~ CH3 H H H
H 3 3 3
H ' H CH3 CH3 H i-C3H7 H
77(~
Herbicidal active ingredients and antagonistic compounds
may be incorporated into the soil either together or separately
and before or after sowing. With acetanilide~, the commone~t
method is to apply them to the surface of the soil immediately
after sowing, or in the period between sowing and emergence of
the young plants. It is also possible to apply them during
emergence. In each instance, the antagonistic agent may be
.
applied simultaneously with the herbicidal active ingredient.
It is also possible to apply the compounds separately - either
the antagonist rirst and then the herbicidal active ingredient,
or vice versa - provided that, if the herbicidal active ingre-
dient is applied first~ not too much time elapses before the
antagonist is applied as otherwise the crop plants may be damaged.
The active ingredient and antagonist may be suspended, emulsified
or dissolved in a spray liquor or may be in granular form, and
may be formulated together or separately. It is also ~easible
to treat the seed with the antagonist before sowing. The
herbicidal active ingredient is then applied on its own in the
usual manner.
2C Varying amounts of antagonistic compound are required for
the ~ame herbicidal acetanilide when it is used in different
crops. The ratio of acetanllide to tetrahydro~ oxazine may
be varied within a wide range; it is dependent on the structure
of the anilide and o~ the tetrahydro-193-oxazine, and on the
crop in which they are used. Suitable ratios of herbicidal
active ingredient to antagonist are from 1:2 to 1:0.05 parts
by weight.
- 15 -
The herbicidal agents according to the i~ven-tion may contain, in a~dition
to acetanilide and tetrahydro-1,3-oxazine, other herbicidal or
growth-regulating active ingredients Or different chemical
structure, e.g., 2-chloro-4-ethylamino-6~isopropylamino-1,3,5-
-triazine, without the antagonistic effec~ being impaired.
The agents according ~o the invention, or, when applied
; separately, the herbicidal active ingredients and the antidote
are applied ~or instance in the form of directly sprayable
solution~, powders, suspensions ~including high-percentage
aqueous, oily or other suspensions), dispersions, emulsions,
oil diqpersions, pastes, dusts, broadcasting agents, or granules
by spraying, atomizing, dusting, broadcasting or watering. The
forms o~ application depend entlrely on the purpose for which
the agents are being used; in any case they should ensure as
~ine a distribution o~ the active ingredient as possible,
For the preparation Or solutions, émulsions, pastes and
oil dispersions to be sprayed direct, mineral oil ~ractions of
medium to high boiling point, such as kerosene or diesel oil,
further coal-tar oils, and oils of vegetable or animal origin,
2C aliphatic, cyclic and aromatic hydrocarbons such as benzene,
toluene, xylene, pararfin, tetrahydronaphthalene, alkylated
naphthalenes and their derivatives such as methanol, ethanol~
propanol, butanol, chloro~orm, carbon tetrachloride~ cyclo-
hexanol, cyclohexanone, chlorobenzene~ isophorone3 etc., and
strongly polar solvents such as dimethylrormamide, dimethyl-
sulfoxide, N-methyIpyrrolidone, water, etc. are suitable.
- 16 ~
,
770
Aqueous formulations may be prepared from emulsion con-
centrates, pastes, oil dispersions or wettable powders by
adding water. To prepare emulsions~ pastes and oil disper~ions
the herbicidal active ingredient and/or antidote as ~uch or
dissolved in an oil or solvent may be homogenized in water by
means o~ wetting or dispersing agents, adherents or emulsifiers.
Concentrates which are suitable for dilution with water may be
prepared from herbicidal active ingredient and/or antidote,
wetting agent, adherent, emulsifying or dispersing agent and
possibly solvent or oll.
Example~ of surfactants are: alkali metal, alkaline earth
metal and ammonium salts o~ ligninsulfonic acid, naphthalene-
sulfon.ic acids, phenol~ulfonic acids, alkylaryl sulfonates,
alkyl sulfatesj and alkyl sulfonates, alkali metal and alkaline
earth metal salts o~ dibutylnaphthalenesulfonic acid, lauryl
ether sulrate, fatty alcohol sulfates, alkali metal and alkaline
earth metal salts of fatty acids, salts of sul~ated hexadecanols,
heptadecanols, and octadecanols, salt~ of sulfated fatty alco-
hol glycol ethers, condensation products of sulfonated naphtha-
2C lene and naphthalene derivatives with formaldehyde, conden-
sation products of naphthalene or naphthalenesulfonic acids
with phenol and ~ormaldehyde, polyoxyethylene octylphenol
ethers, ethoxylated isooctylphenol~ ethoxylated octylphenol and
ethoxylated nonylphenol, alkylphenol polyglycol ethers, tri-
butylphenyl polyglycol ethers, alkylaryl polyether alcohols,
isotridecyl alcohol, ~atty alcohol ethylene oxide condensatesj
ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxyl-
ated polyoxypropylene, lauryl alcohol polyglycol ether acetal,
.
77~;)
sorbitol esters, lignin, sul~lte waste liquors and methyl
cellul~e.
Powders, dusts and broadcasting agent3 may be prepared by
mixing or grinding the herbicidal active ingredient and/or anti-
dote with a solid carrier.
Granules, e.g., coated, impregnated or homogeneous gra-
nules, may be prepared by bonding the active ingredients to
solid carrier~. Examples of solid carriers are mineral earths
such as silicic acid, silica gels, silicates, taIc, kaolin,
lG Attaclay, lime~tone, lime, chalk~ bole, loess, clay, dolomite,
diatomaceous earth, calcium sulfate, magnesium sulrate, mag-
nesium oxide, ground plastics, fertilizers such as ammonium
sulfate, ammonium pho~phate, ammonium nitrate, and ureas, and
ve~etable products such as grain flours, bark meal, wood meal~
- and nutshell meal, cellulosic powders, etc.
The formulations contain from Ool to 95, and prererably
0.5 to 90, ~ by weight of herbicidal active ingredient and
antidote. Application rates of the herbicidal active ingredient
are from 0.2 to 5 kg of active ingredient per hectare. The
2C herbicidal active ingredient is applied either together with
or separately from the antidote in such a manner that the
ratio o~ herbicidal active ingredient to antagonist is from
1:2 to 1:0.05 parts by weightO
Example~ of formulations are given below.
I. 40 part~ by weight o~ a mixture of 4 part~ by weight
o~ 2-chloro-2' 9 6'-dimethyl-N-~pyrazol-1-yl-methyl)-acet-
anilide and 1 part by weight Or M-dichloroacetyl-4,4-di-
methyltetrahydro-193-oxazine i~ intimately mixed with
- 18 -
.
4~77~
10 parts of the sodium salt of a phenolsulronic acid-ure~-
-formaldehyde condensate, 2 parts Or silica gel and 48 parts
Or water to give a stable aqueous diqper~ion~ Dilution in
100,000 parts by weight Or water gives an aqueous di~persion
contalning 0.04 wtZ o~ active ingredient ~ antidote.
II. 3 parts by weight of a mixture o~- 1 part by weight of
2-chloro-2',6'-dimethy]-N-(pyrazol-1-yl-methyl)-acetanilide and
1 part by weight of N-dichloroacetyl-4,4,6-trimethyltetra-
hydro-1~3-oxazine is intimately mixed with 97 parts by wei~ht
of particulate kaolin. A dust i~ obtained containing 3% by
wei~ht Or active ingredient + antidote.
III. 30 parts by weight of a mixture of 1 part by weig~t of
2 chloro 2'-methyl-6'-eth~l-N-(1,2,4-trizaol-1-yl-methyl)-acet
anilide and 2 parts by weight of N-dichloroacetyl-2-ethyl-
-4,4,6-trimethyltetrahydro-1,3-oxazine is intimately mixed
with a mixture consisting of 92 parts by weight of powdered
silica gel and 8 parts by weight of para~fin oil which has been
sprayed onto the surface o~ this silica gel. A formulation is
obtained having good adherence.
2C IV. 20 parts by weight of a mixture Or 8 parts by weight of
2-chloro-2'-methyl-6'-ethyl-N-(pyrazol-1-yl-methyl)-acetanilide
and 1 par~ by weight of N-dichloroacetyl-2-n-propyl-4,4,6-tri-
methyl-1~3-tetrahydro-1?3-oxazine is intimate~ly mixed with
2 parts of the calcium salt of dodecylbenzenesulfonic acid,
8 parts of a fatty alcohol polyglycol ether, 2 parts of the
~odium salt of a phenolsulfonic acid-urea-formaldehyde conden-
sate and 68 parts of a paraffinic mineral oil, A stable oily
dispersion is obtained.
-- 19 _
, ` 13~4~77C3
V. 20 part~ by weight Or a mixture of 10 part~ by weight
of 2-chloro 2',6'-dimethyl-N-(4~5-dichloroimidazol-1-yl-
-methyl)-acetanilide and 1 part by weight Or N-dichloroacetyl-
-4,4-dimethyltetrahydro-1,3-oxazine is dissolved in a mixture
con~isting of 40 part~ by weight o~ cyclohexanone, 30 parts by
weight Or isobutanol, 20 part~ by weight of the adduct of
7 moles of ethylene oxide to 1 mole of isooctylphenol, and
10 parts by weight Or the adduct of 40 moles of ethylene oxide
to 1 mole o~ castor oil. By pouring the ~olution into 100,000
p~rts by weight of water and finely di~tributing it therein, an
aqueous dispersion is obtained containing 0.02% by weight of
active ingredient + antidote.
The influence of various representatives of the agents
according to the invention (herbicidal active ingredient + anta-
gonist) on the growth of unwanted and crop plants compared with
that of agents con3i~ting o~ the same herbicidal active ingre-
dients and an already.known antagonistic compound having a
: chemical structure similar to that Or the antagonist8 in the
agent~ accoL~ding to the invention is demonstrated in the following
2C biological examples. The experiments show that tolerance of the
herbicidal acetanilides is improved, without the herbicidal action
bein~ impaired, when they are combined with the ~e~rallydro-
-1,3-oxazines.
The series Or experiment~ were carried out in the greenhou~e
and in the open.
I. Greenhouse_~periment
:Plastic boxes 51 cm long, 32 cm wide and 6 cm deep were
filled with loamy sand (pH:6) containlng about 1.5~ humus.
- 20 -
: : -
~4770
Indian corn (Zea mays) or wheat (Triticum aestivum) were so~n
~hallow, in row~, in this ~ubstrate. Echinochloa cru~-galli and
Alopecurus were scattered at random a unwanted plants. The
non-sterilized soil also additionally contained viable weed
seed~ which contributed to the weed population. A ~ield with
crop plant~ growing in it and infe~ted with weed~ was thus
simulated.
The active-ingredients and antagonists were applied
separately and in the mixtures given below. They were emulsified
or suspended in water as vehicle and the liquor ~prayed through
finely distributing nozzles onto the soil surface, either imW
mediately a~ter sowing or prior to emergence Or the test plants.
In some cases, the agents were also incorporated into the soil
before the crop plants were sown. After sowing and treatment
the boxes were sprinkler-irrigated and covered with transparent
plastic hoods until the plants emerged. These measures en~ured
that the plants germinated and took root uniformly. The boxes
were set up in the green~louse at from 18 to 30C.
These greenhouse experiments were monitored until 3 to
2C 5 Indian corn leaves had developedg No more damage due to the
herbicidal agents was to be expected af~er this stage, a fact
which was confirmed by the experiments in the open. The scale
for assessing the act1on of the agents was 0 to 100, 0 denoting
normal emergence and development of the plant~, with reference
to the untreated control, and 100 denoting non-germination or
withering of the plants. It ~hould be borne in mind here that,~
for instance in Indian corn, odd crippled or retarded plants
may occur even under completely normal condition~ and without
any chemical treatment.
- 21 -
'70
.. . . .
II, Ex~eriments in the open
These experiments wererun o~ snall plots in loamy sand and
loam (pH: S to 63 with a humus content of 1 to ~5%. Pre-
; emergence treatment took place either immediately after the
crop plants had been sown, or at the late~t 3 day~ later.
The weed flora was mad~ up of various species and was naturally
occurring. However, only the dominating representatives have
been included in the tables. Active ingredients and antagoni~t~,
and combination~ thereof, were emulsified or suspended in water
as vehicle and applied by means of a motor-driven plot spray
mounted on a tractor. Where no rain fell, the plots were
sprinkled to ensure normal emergence of the crop plants and
weeds. All the experiments were run for several months, thus
enabling the development o~ the crop plant up to seed formation
to be observed. Assessment of the action of the agents was
; also made on the 0 to 100 scale.
Results
As a result of the shallow sowing Or the crop plants and the
more favorable conditîons for herbicidal activity, the damage
2C caused by the herbicidal active ingredients in the greenhouse
was much greater,than in the open. The test conditions ror
the antagonistic compounds were there~ore severer in the green-
house than in the open.
,
Where the antagonistic -tetrahyd;rc;-l, 3~oxazines are
applied on their own9 they have a scarcely perceptible effect~
if at all, on the germination and growth of the unwanted and
crop plants. This is also apparent at application rates sub~
stantially higher than those required ror antagonstic ef~ects.
~ 22 -
` ` 114~47~0
.' .
However, the -tetrahydro-1,3,,oxazines :reduce t~le ~hyto~oxicity of
the herbicidal acetanilides Or the ~ormula I to crop plants
such as Indian corn and cereals to a con~iderable extent and
in some cases eliminate it completely. It was ~ound that in
the case of herbicidal compounds ~Ihich are less aggressive to
crop plants it is suf~icient to add smaller amounts of anta-
gonistic compounds or antagoni~tic compounds having a lesser
antagonistic action.
Table 1 List of plant name3
10 Botanical name Abbreviation in Common name
tables
AlopeGurus myosuroides slender foxtail
Chenopodium album lambsquarters
Echinochloa crus galli Echinochloa c.g. barnyardgrass
Galinsoga spp. gallant soldier
Hordeum vulgare barley
Matricaria Anthemis spp. chzmomile
Triticum aestivum wheat
Zea mays Indian corn
2C
- 23 -
.
:
E ~ ~ O
.. :
~ ~
d
1 0 0 ~ '
',c~ X ~:
~: \ I ' ._ .
X
C:~ V C) C~
., V~
::
. ~ ~ ~ ~
~: :~ X ~. ~ ''''
. C~ ~ ~)
C~
, ~ . ~ 5:
~ . . C~ O X
2C ., ~ z~zl~ z~fi~ z~
s 1.
,,s,~, : . ,
~: r~ ~ . . ' ~ ¢
C~J
E~
-- 24 --
` ~ 1144'7~70
~ .'
1~1 O :J N
N O
.,
~u
'
.
~ -~
, ,~C
. ''
~: .
. ,~
X
,t
. C~
2C '~ ~ Z/~
:Z
, :
.
C~ o .
N ~d
a) & 1~ H
r~~ rl
~ U~
~ . 1,
-- 25 --
~ 7
"
,
:
a)
U)
U~
S: ,~'J '
N
U
h "~ ~
~o ~ X ~ ~ ~ r~ ~.
. C~ )
~ . ~: .,1
C~ ~1 C~
. ~, . l .~
u~ nl . .
~rl X . X
. .' ~. ~ .
~ ~ : X C,); X ~ -- X S ~Z~
2C ~" . .
.c . .
~.,, . 0
. h
' ~ ~ a ~ h
", : Z . ~ , .
p
d
' ,
-
-- 26 --
7~
, . -
(~ o ooIa~ggoOo,CDOO OOIOOIOOICIOIOIOI
~ o o ~ V~ o ~ o~ o o o o ~ o o ~ o o . o ~ o ~ C,
% ~n ~ '
-s~
N~ Q. I
(3) ttJ E~ I I
~3 X
r-l O
F-~ ~ o~ ~ I ~ o o o o I c~ 8 o o o I o c I oO o I o , o I o I _ I
~, ¢ ~. . I , . . . ...... . . .
h .~ j l ¦ ¦
I ~ a) I I ~ I I
~ o, c o ~ o o I ~ u~ t u~ o , c
h ~ ~~ t_ l .- ~ l ~ .- l - ~ l ~ ~rJ l r~ I r~
C) bO ~ h ~ I '
H a~ ~rl h
S SOO I ~ C OrJu~ I ~ ~ O ~O I ~O I ~ C I I r~ I r~ I I
O ~ r ~ 1 o ~r I ~r ~ t I ~ I I I I
~ ~ ~ P, ~o ~ rJ I 0 ~ N 0 0 1 O O t~ O r~ I o rl I O rJ I ~ I o I O I O I
Ei~rl a) , , .
~: h I . I ' I
~ rl ' ~ ' I' I I I I I I . I
O ~--bO O 3
~rl ~I h ~ O
~s~ ~o ! ` i~
al ~; h
~ ~) I I I I I I I I I
3 ~ri rl I I I I I I I I I
,1 ,D-r~ h ^ I I I I I ~ I I I
_ 27 ~
.
b~ ~ 1
c~ l ~
o l o l c~ l o j o l o
t I !
l l l l l
r~ t t, `,, .
l l l l l
.
~n~ ' ! ' ' I
b~ I 1`1 1 i
t~
a) , ., , , ,
~ 3 C~ hO I O I O ~ O I O .
1 0 c~ ~ l
~¢~ ', !~
., I 1 ~ ~
, , , , ,
a I I ~ ~ ~
E o ¦ c I a j o j c~ j o
~ l l l l l
o
h I i i i i
., , , I I a~
I i I I I a,
l l l l l ~
l l l l l ~
I_ l l l l l ~ rl
~ . O i O i O i O I O i O b0 3
¢IJ l ll l l
2~ . .~ I~, I I o
~ . I I ~ ~4
~a ~ .~
o ~ I ~ ~ , ,
--~~d Q.~ j N ~ ~ ! ~ i ~ E~
~a ! ~ ~ h
s:: l l l l l ~1
O l l l l l n~ ~
i j i j E ~:
~i p-rl h I I I I ~ I I ~ I I I
D h ~ hO ~ O
~ I I I I O
~ x~.,, I, 1 t I o
- 28 -
~4~v
h --l
O
t~
I
~: a) , I , I ,,, I I ,
td bOl l l l llll ll ll ll
~ ~ ~ . ~ I I I I ~ I I I
H F~ ~
~,V bO~td ! I i
.a a) ~ P~
oo I o I ooo I oo I oc~o I oo I oooo I oo I ooco
tn ~ asoo I I ooo I oa I ooo I oo I oooo I oo ~ oooo
a bO ~ o
,~ h ~ ~ ~t
t~ri I ~ I I I I I I I
~ ~ ~a ~s, , . , , . . . ,
~ a) c ~ c~
t~ ~ ~ ~ ~' ' ' ' ' ' I ' ' .
10~ R. In , t t
C~ V
~d ' ' ' O ' ' ' ' I
t5 ~ 0~ I . I
~rl N ~ tlJ U~
~ x ~ ~ ~ t~ t~ I ~ o~ o ~ o ~ C ~ ~ ! ~ ~ o o ~ O L I O O U~ O I
o r~ o t~ I ~ I I I I I 1
S ^ h CJ
o o l l I I I , I
h
a)~a
~s v~ ~ , !L U~ ! !u~ !
h h h I I ~ L~ O I I t'`J 11~ 0 1 1 t~l O t~l O I I t~J 11'. 0
Il) ~ I_ O O I O I ' I O O I ~ C I O O I q ~- D I O O I
~I) ~ ~ I O O t~ I O O ~ I C r~ O t~ I O O t~J I
O V ~ .C ~ J 1 3 1 + + + I s t~J I + ~ + I r~ t~J I + + + ~ I I ' + I I
I I 000 1 1 000 1 1 0000 1 1 0~00 1
.C J~ ¢ l_
U~
.
2C~ ~o t~
bO :~ ~'
0 o ~n
S~ i ~ I I I I I I I . I
a) bO o
O h 0 ~ II ~ I ~ I I I r~ I i ~ r~ I I ~ ~, I
O ~ bO ~ ~ I li . I I I I i
. h ~c) ! ! ! t I !` i ! i
~_~ ra ~ I ~ I t
U~ ~ri rl I . I I I I I I I O
c) o ~i -
ri h .
~ ~ ~¢ ! I ! ¢ ,t tri ll tri ! c~ ! c~ i C ! ~, i
-~ , , ., . I
t I I t i 0 t
. ~ 29 ~
7~
.
, , , , I ,, I
.. . . .
, .
l l l l l l l l l
.
~ C~
(d C O I O O I O O i C O O I Cl~ O I Cl ) Cl ) t~ I ~1 ) I L~ I C3
a. o o o I o o I o o I o o o I a~ o I c~
l l l l l l l l l
._
S I I I I I I t ~ . I
I I ~ I I I I I I
3 ~1 l l l l l l l l l
~) . I I I I 1' 1 1 1"'.
1:
l l l l l l l l l
~ l l l l l l l l l
~ ~ ~q l l l l l l l l l
o o I o o I o In I o o o I o ~ o I Q I U~ I O
n
~ I I ! 1 ', , I I !
C~ ~ , . . . . . . .
, ,. , , , , , , ,
, , , , , , I ,. , a~
l l l l l l l l l
a~ , ., , , , , , , , o
h
t~ I I
r~ I ~ U~ I , O ~10 ~ O U~ O ~ a
. ~ O O I > I~ I O O I J> ~ I O O I '- t ~ I O I ~ I O I ~ ~ bl)
S O i I O O I ~ I ~1 0 N I ~ I O ~ C I ~ I O I ~ O ~li
--1 ~ r~ /r 'r I rl N I ~ I ~ I I tU I ~ ~ ~ I ~1 I -1 1 ~-1 I ~ ~ Ei 1/~
I 00 1 1 000 1 1 000 1 1 0 1 1 00
~X I ~ 1 1 o
¢ ~ I ~ ~I I I ~1 ~ ~ I I 1 ~ ~U I I ~ I I ~ s~
l l l l l ll l l O I~~
I I . I O I II I I C ~
2C ~I l l l l ~ ~ h
I I I . I I I I, I ~ ai
bO O ~ i i ~ I I ~ I i ~ h: F.
~J ~ ~ I I I I I I I I ~ ~
E , ~ a~ h
C l l l l l l l l l ~ E
o I I ~ ~ a~
~_ ~ C I I I ~ I i I I I I O O
c~
~rl ~ ~ I I I I I I i
R rl h I _ I _ I H I
p~ ~) bl) ~ I I i O O
ttia~ c) C I i I II I ~ I I O
I-rl . ~1
- 30 -
'770
.
., .
boD . t `
o , o o
~: ~ ~o,, ., o, o,
n l-t I ~ r1
1:: r~ t
r1 b(1 ~ I .
~1 X p~
N ~ O~ n.
rl
:~ `h tq
--o Ia) ~ c) E~ O O O I O O O O
Z a) h~ ~ h S o o o t I O O O O
I ~t ~ ~ l
r~ l
s ~a ~ ¢
' S X~
J~-~ h~ a) l
. I
a
)-rl
10 --J~ S u~ ~ p, ~s a~ o o I I ¢ I o
~J ~-rl ~1 S .
O ~ I
O O ~ t
C) C r~ ~ 3 1 o t~t ~t L'~
N ~rt ~ ~ . I
~ a o ~
O H ~ l l ~a
al ~ h l O
c ~) 5 ~ h
~ ~ C)F~ O O O I ~ l O O . U~
r r r~ ~ ~J 1~ 5 0 0 0 1-
O r~
~I) ~ 11~ ~.Y 5
.~ 7 ¢ 11_ l ~d
~-r~ l o 1-
. ~ c
I c)c) l
2 c ~ r 5 ~ h
n I . c
I ~:
~L) ~) r l ~ ~ l ~ ~L)
O :1 l bO t)
a.) E~ C~ bO O ~ I t~ ~ C
O ~ î ' E~ bO'
h ~ o I . ~) h
u~ ¢ c~ 5
. I ~ .
tl~ C . I ~1 C
to r~ ~r~ I ~ ~
~1> rl ~ al l
rl h ¢ . I ~: -
5~ h ~ W l O O
-- 31 --
7~0
I
,...... , , .
o , I l
.,, , , ,
a~ a~ u~ I I I
N ~h . ~ I ~ N N L~ .
a~ ~ ~ o ~c~ ~ I ~ I ~cr~
~t X bO ~ o h
O td ~ ~ ~ I ~ I
a~ I e ~ u~
h r~ a O O
a~ ^ a a~
~ o ~
~ h a 3 l l l
~ c ~ e ' ' '
I I .
a~s o
r~ h J~ ~ ~
~ a) ~h a~ ~ l-~ I N Ir~ Ln
I
t
~a) , .
a) ~ u~
l l l
(~ ~) O
E~ S ~ ~ ~ a~
h
rl ~r h P. h ~ N ~.0 1 2 ~ ~
c) .~ o o ~ l l I
~3 h ~:
n I ~ C~ I ~ ~
h ~ r
al ~,~ a~
r~ ~ ~ ~
~ ~ ~ I U~O , O I I O
rl h t o ~10 ~ I I o
o ~ . ~ '~ . t o o o o ' ~ t o o
a) h ~ ~ ~ I . o ~
~ r-l e ~ ~o t ~ 1 1 ~ ~
~ ~ ~ ~ l l l
h c.) ~ ¢ LJ
a~- l a~
rO~ h c) i ` ! !
2C ~ Z ~rl I I t
l l l
a) ~: ~ ~
a) ~ b~ o
u~ O h ~0 O
P.
h-~ O ~
a) ~ c~ l l l .
~h I ! !
l l l
a~ I I .
~ l l l
c~ ~ I I
o~ r~ ; ~ a) ! ! I
- !3 !a !~
-- 32 --
'77~
vi
o o
,
x a)~ ~ , , .
o 5 ~ ~ ~
~ l l l l .
~ ~ e p, o CJ~ ~ ~ i o i ~ ,
~ ~ ~ o~ I I I cJ~ I a~ .
s~ i
. ~ o I 1 .
~ l l l l
10 -~ -'' =' ~ . j j j j .
.
o
o~ ~ ' I I !
D ~ D~ e _ ~ _ j ,, j , , , ~0 ~ I ~ a~ o
~ ~ l l l l
t, Q~` 2 ~ I i I i
, ,, I ,
! I i N j ~
o ~: rd h I t t ~ ~ 4 1 ~ C~ Ui
. 0~ 1 o i ~. I ~ T ii G o+ o 0
~ 4-l r~l ~ ~1 ~J ~\ I 3 1 ~ ~ O O O I O O O E~ u~
¢~J ~ b ~ 4r~ a a
~ o ~ l l l l
2 C ~ ~ rl r~ t I ~ rl h
I I ~ I I ~ C~
,n ~ o ~ t i ~d ¦ t ~ r ~
rl rl LH bO O . I I h i S-. h
~1 ~ 0 0 Q I I /~ I ~ rl I I
Q~ O I ~ h I I h O h
~ r-l (a ¢ ~) I I D~ .
O (1) ~ ~ r~l
o
~rl r~ ~ I I I O O
c) ~a l l l l
a~ ~ r~ ~ ~1) . I I I I I i I )
D ~ri ~ I t , I " , ~ o o
.
. .
- 33 -
