Note: Descriptions are shown in the official language in which they were submitted.
- 1 -
Case 5-11795/~
~ .
It is known rom the prior art that substituted
phenoxy-propionic acid derivatives can be used as :
herbicides (see R. Wegler, Chemie der Pflanzenschutz-
und Sch~dlingsbek~mpfungsmittel [Chemistry of plant
protective agents and pesticidal compositionsl, Springer-
Verlag, Heidelberg, New York, 1970, Volume 2, pp. 278 ff,
and more recent patent applications, such as German
Offenlegungsschriften Nos. ~,223,894 an~ 2,613,697, and
B~lgian Patent Application No. 855,~94.
The herbicidal effectiveness of the known compounds
does not however always satisfy requirements, particularly
when these compounds are applied in small amounts.
Furthermore, such compounds are frequently not suf~iently
selective with regard to the cultivated plants to be
protected. Attempts have already been made to overcome
the stated shortcomings of the known propionic acid
derivatives by incorporation of suitable functional groups
in the ester part o~ the molecule. In conn ction with
this work, there have also become known substitut~d
phenoxy-propionic acid derivatives which carry in the
ester part of the molPcule a~ additional alkoxycarbonyl
(COOalkyl) or a carboxyl group (COOH) (see German O~fen-
~,
..~
.
.; . , . , - .
.
~ 3~ ~ .
- 2 -
legungsschift No. 2,628,384.
The present invention relates to novel esters of
O~(pyridyloxy~phenyl)-lactic acids having a herbicidal
and plant-growth regula~ing action, to F)rocesses for
producing these esters, to compositions containing them
as active substances, and to the use of these esters,
or of composition~ containing them, for combating weeds
and for regulating plant growth.
Surprisingly, the active substances of the formula I
according to the invention are superior to the hitherto
known compounds of the prior art which have a similar
structure and which are substituted in the ester part
by an additional ester functionn The novel active sub-
stances are distinguished by a high activity against
numerous weeds. Furthermore, they are selective with
respect to important cultivated plants, for example
wheat, soya bean, cotton and sugar beet.
The novel active substaQces of the present invention
are 0-[4-(5'-halogenopyridyl-2'-oxy)-phenyl)-lactic acid
esters and correspond to the formula I
~al_~-O~ O-C~-CU-Y-Z-CO-Q (I)
in which
"Hal" is a halogen atom,
X is hydrogen or a halogen atom,
Y is an oxygen or sulfur atom,
Z is a Cl-C4 alkylene group which is unsubstitutPd or
substituted by methyl, ethyl, cyano, methyLcarbonyl
or by a group -COQ, :
P 1~ SR2 or -NR3R4, wherein
.
~; ' ' ~ ' '. '
!
~L43~
Rl, R2, R3 and R4 independently of one another are each hydrogen
or C1 to C~-alkyl.
The novel compounds of the formula I are produced by
known reactions of chemical synthesis, for example according to
one of the following reaction patterns:
(a) X CH3
Hal ~ ~ O OH ~ Hal-CH-CO-Y-Z~CO-Q~
N
A correspondingly substituted 4_(s t -halogenopyridyl-2'-oxy)-
phenol is reacted, in the presence of a base as an acid-binding
agent, advantageously in an i~nert sol~ent, w~th an appropriate
lQ derivative of 2-halogenopropionic acid, where "Hal" is a halogen
atom, preferably chlori~ne or bromi`ne, and X, Y and Z have the
meanings defined under the formula r.
4-(5'-Halogenopyridyl-2'-oxyl-p~lenol is o~tained by
reaction of appropriately substituted 2,5-dihalogenopyridines
with hydroquinone in a manner known per se,
~' .
," ~1
.
,, :
'
38
k: ~
The derivatives of ~-halogenopropionic acid are
obtained in a manner known per se by reaction of
hydroxycarboxylic acid, or mercaptocarboxylic acid
derivatives, with 2-halogenopropionic acid halides.
b) X
Hal ~ ~ OC3-COOYH ~ Hal-Z-C0-Q~
The 0-[4-(5'-halogenopyridyl-2' oxy)-phenyll-lactic
acids or -thiolic acids known from the prior art (see
for example German 0ffenlegungsschrift No. 2,546,251 or
No. 2,732 9 846) are reacted in a known manner, in the
presence of a base as acid-binding agent, with esters
of halogenocarboxylic aci.ds. These esters correspond
to the formula
Hal - Z - C0 - Q
wherein "Hal?' is a halogen atom, preferably chlorine or
bromine, and Q and Z have the meanings defined under the
formula I, and are, for example, esters, thioesters or
amides of chloroacetic acid, bromoacetic acid, a-bromo-
propionic acid, ~-bromobutyxic acid, ~-chloro- or -bromo-
propionic acid, ~-bromobutyric acid, ~-bromobutyric
acid, and so forth.
c), X
~81 ~ ~ 3 base
~ ~ 0 ~ 0CH-C0Hal + HY-Z~C0-Q ~
In this modification of the above process, acid
halides of 0-[4-(5' halogenopyridyl-2' oxy)-phenyl]-
lactic acids are reac~ed, in a manner known per se, with
esters of hydroxy- or mercaptocarboxylic acids. Examples
;: ~
... . . . . .
.. ~ , . . .
?
` ~
of acids of this type are lactic acid, glycolic acid,
~-hydroxypropionic acid, ~- or ~-hydroxybutyric acids,
and also the corresponding thiolic acids, thioglycolic
acid, thiolactic acid, and so forth.
The reactions are preferably performed in a solvent
which is inert to the reactants. Suitable solvents are
solvents belonging to the widest variety of classes of
substances, such as aliphatic and aromat:ic, optionally
chlorinated hydrocarbons, for example ethylene chloride,
and the like, as well as polar organic solvents, such
as ethers, ketones, amides, stable esters, for example
methyl ethyl ketone, dimethoxyethane, dimethylformamide,
dimethyl sulfoxide, tetrahydrofuran, and so forth.
As basic acid acceptors for the reaction with halogen
compounds, it is possible to use aqueous alkali metal
hydroxides, such as KOH and NaOH, and also further
customary basic substances, such as carbonates (K2CO3,
NaHCO3), alcoholates (NaOCH3 and potassium tert-butylate),
but also organic bases, such as triethylamine, and so on.
The free propionthiolic acid (Y - S) to be used
for example as starting material in reaction pa~tern b),
and also the production ~hereof from the correspon~ing
propionic acid halide with hydrogen sulfide, Na2S or
NaHS, in the pre~ence of a basic acid acceptor, is the
subject matter o a pending patent application. The
a-~4-(3',5'-dichloropyridyl-(2')-oxy)-phenoxy]-propion-
thiolic acid produced by this method ls an oil having a
refractive index n21 = 1.5787, which melts at 85-87C
after crystallisa~ion.
The Examples which follow illustrate the production
of some active substances of the formula I according to
the invention. Further final substances o~ the formula I
~ 4L3~ :
~,~
which are produced in a corresponding manner or by
another of the methods mentioned in the text are
subsequently listed in tabular form.
Example 1
0-[4-(3',5'-Dichloropyridyl-2'-oxy)-phenyl]-thiollactic
acid methoxycarbonylmethyl)-ester
Cl
Cl ~ 0 ~ OCH-C=0
SC~2C~OcH3
5.8 g (0.055 mol) of thioglycolic acid methyl ester
and 5.5 g (0.055 mol) of triethylamine are added to
17.3 g (0.05 mol) of 0-[4-(3',5'-dichloropyridyl-2'-oxy)-
phenyll-lactlc acid chloride in 130 ml of toluene. A~ter
the exothermic reaction has subsided, the mixture is
heated for 2 hours at 40C. The reaction is then cooled,
the salt is filtered off, and the filtrate is concen-
trated by evaporation and filtered in chloroform through
a short silica gel column. Concentration by evaporation
leaves 13.5 g (64.8 % of theory) of the title product
in the form of oil having a refractive index n25 = 1.5580,
and this product melts at 65C after recrystallisation
form ether/petroleum ether.
The acid chloride required as starting material is
obtained as follows: ,
30 ml of thionyl chloride is added to 26.8 g (0.082 mol)
of 0-[4-(3',5'-dichloropyridyl-2'-oxy)-phenyl]-lactic
acid and, after the evolution of gas has subsi~ed, the
mixture is heated to 50C. After two hours, the reaction
mixture is concentrated in vacuo; 100 ml of toluene
.
: . . .: ' . ' . . .
. : .
. .
~ ` 1 f~ 3~ 2
is added and the mixture is again concentrated by evapor-
ation. There is obtained as product a dark-brown oil,
which slowly commences to crystallise. The yield is 25.9 g
(86.7% of theory) o 0-[4-(3',5'-dichloropyridyl-2'-oxy)-
phenyl~-lactic acid chloride having a melting point of 45C.
0-[4-(3',5' Dichloropyridyl-2'-oxy)-pherlyl]-thioLartic
acid-(l"-methoxycarbonyl-ethyl)-ester
, .. . ,. .. _ _ _ . ____ . ~
~1
Cl ~ 0 ~ -CH-C0-SCH-COOCH
- 3
12.0 g (0~035 mol) of 0-l4-(3',5'-dichloropyridyl-2'-
oxy)-phenyl]-thiolactic acid is dissolved in 50 ml of
methyl ethyl ketone, and 5.5 g (0.04 mol) of potassium
carbonate is added at room temperature. The temperat~re
rised ~o 32C as gas is evolved. After 10 minutes, there
is added 4.25 ml (0.038 mol) of 2-bromopropionic acid
methyl ester. The reaction is exothermic and the tem-
perature rises to 45C. The reaction mixture is filtered
after 10 minutes and, after concentra~ion by evaporation
and drying under high vacuum at 55C, there is obtained the
pure title product having arefractive îndex n22 ~ 1.5779;
yield: 13.8 g (91.4 % of theory).
The propionthiolic acid required as starting product
is produced as follows.
17.2 g (0.0496 mol) of 0-(4-(3',5'-dichloropyridyl-2'-
oxy)-phenyl~-lactic acid chloride, produced as in
Example 1, is added dropwise to a mixture of 8.9 g of
KOH in 4.9 ml of water and 75 ml of dimethoxyethane, which
has been saturated at 10-15C with H2S during vigorous
stirring. As the dropwise addition is proceeding, the
temperature is kept at 10C using an ice-bath. The
reaction mixture is subsequently stirred for 30 minutes
: ' :
.. ,
g ~ 43~3Z
,~
at room tempera~ure, and is then poured into 150 ml of
ice/water. The pH value of the cloudy brown solution
is adjusted to 1 with concentrated HCl, in the course
of which there precipita~es a brown oil, which is taken
up in methylene chloride. The organic phase is applied
directly to a small silica gel column and is washed
through with methylene chloride. The light yellow solution
is concentrated by evaporation to yield a clear orange- ;
coloured oil, which crystallises on being triturated with
petrolewm ether. The result is 16.8 g of a-(4-(3',5'-
dichloropyridyl-2'-oxy~-phenoxy)-propionthiolic acid
in the form of yellow crystals having a melting point
of 85-87C.
Example 3
0-[4-(3',5'-Dichloropyridyl-2'-oxy)-phenyl~-lactic acid-
(l"-ethoxycarbonylethyl) ester
Cl
Cl ~ _ ~ 0cH-co-o~H-cooc2Hs
12.8 g (0.05 mol) of 4-(3',5'-dichloropyridyl-2 -oxy)-
phenol with 8.3 g (o.o6 mol) of potassium carbonate in
50 ml of methyl ethyl ketone is heated for one hour at
boiling point. There is then added at 50C 13.2 g
(0.052 mol) of 0-(2'-bromopropionyl) lactic acid ethyl
ester, and the reaction mixture is stirred at 55C for
12 hours. The brown suspension is subsequently filtered,
and the filtrate is concentrated in a rotary evaporator.
The brown oil is chro~atographed with petroleum ether
through a small silica gel column to obtain 10.9 g
(52.7 % of theory) of the title product having a refractive
index nD = 1.5424.
. - ~ .
. . : ' ' . -
.; , .
L3
q
,~
The 0 (2'-bromopropionyl)-lactic acid ethyl ester
of the formula
CH3 i 3
Br ~ CH ~ C0- 0 - CH - COOC2H5
which is used as an intermediate product, is obtained
as follows:
A mixture of 60.2 g (0.51 mol) of lactic acid ethyl
ester and 51.5 g (0.51 mol) of triethylamine is added
dropwise at 10-15C to 110 g (0.51 mol) of 2-bromo-
propionic acid bromide in 250 ml of toluene. The whi~e
suspension thus formed is filtered after 15 minutes 9
and the filtrate is concentrated by evaporation. The
residue is distilled in vacuo to obtain at 78C/0.6 mm
93.6 g (72.5 % of theory) of the ester in the form of
clear oil.
The esters listed in the following Table are produced
in a manner analogous to that described in these Examples.
. ., - . . -, , .
'
.
: ~ ....... , .. ,. ;, - , .. ..
:
`~ /v ~ 3~2
X
Ha l4~ ~--O -CH -CO -Y -Z -CO -Q
~__
No . Hal X Y Z Q Physical
constants
-- .. __ __~ ~ .
1 C1 C1 S C~2 O~H3 nI~5 1. 5580
2 Cl Cl S CH(CH3j OC~I3 n22 1.5779
3 Cl Cl O CH (CH3) C2H5 n22 1. 5424
4 Cl Cl S CH(CH3) NHC2H5 m.p. 113-14C
Cl Cl O CH (t::H3) 2H5
6 Cl Cl S CH2 NH2 m . p ~98 100C
7 Cl Cl C~2 ~H2 m-p. 154 59C
8 C 1 C 1 C2H4 NH2
9 Cl Cl S G2H4 OCH3
C 1 C 1 C2H4 OCH3 2 2
11 Cl Cl O 2 O~I3 nD 1.5489
12 C 1 C 1 O CH2 OH
13 C 1 Cl S CH2 OEI
14 Cl Cl O CHCN C2H5, 2
lS Cl Cl O C~ICOOC~H OC2H5 n~ l o 5339
16 C l C l S CHCOOC2H j OC2~5 n~2 1 . 5 4 61
17 Cl Cl S C~ICN 3C2H5 nD2 1. 5612
18 Cl Cl O CHCOCH3 ~CH3
19 Cl Cl S CHCOCH3 ~CH3 .
Cl H S C~2 ~CH3
21 Cl H C;H2 C~3 22 1 5598
2 2 Cl Cl S CHCOCH3OC2H5 nD2
23 Cl Cl S 2 4 C2HS n~? 1. 5580
24 Cl Cl O CHCOC~I3OC2EI5 nD 1. 5253
Cl Cl S C2H4 NH;~ m.p. 109-10 C
--__ _ ~ ~
:
. ~ . -
:, . . .
.
~ , . . ,: - - . .. . .
- ~ - .
3~3Z
~ ,1
,~
The novel active substances of the formula I are
stable compounds which are soluble in customary organic
solvents, such as alcohols, ethers, ketones, dimethyl-
formamide, dimethyl sulfoxide, and so forth.
The invention relates also to compos-itions having
a herbicidal and plant-growth-regulating action, which
contain a novel active substance of the formula I, and to
processes for the pre-emergence and post--emergence
combating of weeds, and for the inhibition of the
growth of monocotyledonous and dicotyledonous plants,
particularly of grasses, cereals and soya bean plants,
and of side shoots of tobacco plants.
The compositions according to the invention can be
fonmulated in the customary manner.
The compositions according to the invention are
produced in a manner known per se by the intimate mixing
and grinding of active substances of the formula I with
suitable carriers~ optionally with the addition of
dispersing agents or solvents which are inert to the
active substances. The active substances can be obtained
and used in the following ~orms:
solid ~re~rations: dusts, scatt2ring agents, granules
tcoated granules, impregnated granules
and homogeneous granules);
water-dispersible concentrates_of active substance:
wettable powders, pastes and emulsions;
liquid preparat ons: solutions.
The concentration of active substance in the compo-
sitions according to the invention is 1 to 80 per cent
by weight, and when being applied the compositions can
if necessary contain the active substances also at a
lower concentration, such as about 0.05 to 1 per cent.
.
. :
.
: ' ,
i43B~
,~
Other bioci.dal active substances or compositions can
be added to the compositions according to the invention.
In order to widen their sphere of action, the novel
compositions can thus contain, in addition to the stated
compounds of the formula I, for example insecticides,
fungicides, bactericides, fungistatics, bacteriostatics,
nematocides or further herbicides.
Some examples of solid and li~uid preparations are
described in the following in order to illustrate the
production of compositions according to the invention.
Wettable powder
The following constituents are used to produce a) a
50% wettable powder, b) a 25% wettable powder, and c) a
10% wettable powder:
a) 50 parts of active substance,
parts of sodium dibutyl naphthyl sulfonate,
3 parts of naphthalenesulfonic acid/phenol-
sulfonic acid/formaldehyde condensate (3:2:1),
29 parts of kaolin, and
22 parts of Champagne chalk;
b) 25 parts of active substance,
S parts of the sodium salt of oleylmethyl
tauride,
2.5 parts of a naphthalenesulfonic acid/
formaldehyde condensate,
0.5 part of carboxymethylcellulose,
parts of neutral potassium aluminium
silicate, and
62 parts of kaolin; and
c) 10 parts of active substance, .
3 parts of a mixture of the sodium salts of
saturated fatty alcohols,
. , . . ~ .. .. _,.. . . . .
. . . .
. ~ . . .
~ ' . , .
.,
.
.' , ,' '-, ' ' '
3i~Z
,~
parts of a naphthalenesulfonic acid/
ormaldehyde condensate, and
82 parts of kaolin.
The given active substance is absorbed onto the appro-
priate carriers (kaolin and chalk), and the material is
subsequently mixed and ground with the remaining con-
stituents. Wettable powders having excellent wetting
and suspension properties are obtained. It is possible
to obtain from wettable powders of this kind, by dilution
with water, suspensions having an active-substance
concentration which is suitable for combating weeds in
crops of cultiva~ed plants.
Paste
The following materials are used to produce a 45% paste:
4S parts of one of the active substances of the
formula I,
parts of sodium aluminium silicate,
14 parts of cetyl polyglycol ether having 8 mols
of ethylene oxide,
1 part of oleyl polyglycol ether having 5 mols
of ethylene oxide,
2 parts of spindle oil,
parts of polyethylene glycol, and
23 parts of water.
The active substance is intimately mixed and ground
with the additives in apparatus suitable for the purpose.
There is obtained a paste from which can be produced,
by dilution with water, suspensions of any desired
concentration.
}~uls~on C~n cen C =a t~
The following constituents ar~ mixed together to
. .
.
.. . .
. . .
. .. . . .
- . ~
.' ' . ' . ~ . :
~ ` ' ' ': :
/~ L3~32
produce a 25% emulsiun concentrate:
~5 parts of one of the active substances of the
formula I,
parts of a mi~ture of nonylphenolpolyoxy-
ethylene and calcium dodecylbenzene sulfate~
parts of cyclohexanone, and
parts of xylene.
This concentrate can be diluted with water to give
emulsions of suitable concentration, for example 0.1 to
10%. Emulsions of this kind are suitable for combating
weeds in crops of cultivated plants.
Compositions according to the invention, which contain
as active substance at least one ccmpound of the formula I,
are suitable in particular for selectively combating
monocotyledonous wild grasses, by pre-emergence and
especially post-emergence application, in crops of
cultivated plants, or example in crops of soya bean,
cotton, sugar beet, wheat and other varieties o~ cereals.
The following test methods serve to verify the
suitability of the novel active substances of the formula
I as herbicides (pre- and post-emergence), and to prove
the superiority of them over known active substances of
similar structure.
Pre-emer~ence herbicidal action (inhibition of germination)
Im~ediately after sowing the test plants in seed
trays in a greenhouse, the surace o the soil is treated
with an aqueous dispersion of the active substance, which
has been prepared from a 25% emulsion concentrate, and
from a 25% wettable powder con~aining active substances
which cannot be produced as emulsion concentrates owing
to inadequate solubility. Four di~ferent concentration
.43~
,~
series are used, corresponding to 4, 2, 1 and 0.5 kg of
active substance per hectare. The sPed trays are left
in the greenhouse at 22-25C with 50-70% relative
humidity, and the test is evaluated after 3 weeks, with
the resuLts being assessed according to the following
scale of ratings:
1 = plants have not germinated or have fully died off,
2-3 - very intense action,
4-6 = moderate action,
7-8 - slight action,
9 = no action (as in the case of untreated control
plants).
O-(Pyridyloxy-phenoxy)-laetic acid esters according
to the invention are compared in this test with the
following structurally similar compounds:
Cl c~3
Cl ~ o ~ o-c~-COSC~2-COOC~l3
0-[4-(2',4'-dichlorophe~oxy)-phenyl-thio-lactic acid
(methoxycarbonylmethyl) ester~ known from the German
Offenlegungsschrift No. 2,628,384, Example 3;
Cl~ 3OC~-~OOC~-COOC~}15
0-~4-~2',4'-dichlorophenoxy)-phenyl-lactic acid-(ethoxy-
carbonylethyl) ester, known from the German Offenlegungs
schrift No. 2,628,384, Example 23.
The following plants were tested: barley and cotton,
as well as the weeds Avena a~ua, Alopecurus myosuroides,
Rottboellia exaltata and Digitaria sanguinalis.
. ,
: .
' ' : ~ . : ~
The results are su~narlsed in the Table given
below. :
___ ~ , . ~_
~ ~ 1 ~ Ot Cr~
_~ ~ 1 ~ ~r ~ 1 : ''
_ __ _ _
cn ~ ~ ~ ~ ~ ~ ~
~r a~ ~ ~r ~ ,1 ~ e: a~ o~ 0 ~D f'~ ~1
a~ 1
~o ~ : -
~r ~ ~ l ~ ~ ~ cr~ 1
. :
.
,~ ~1 ~ ~ ~ 1` ~ _1 ~1
~ a~ 1 ~ ~r ~ 1
___ .
5~ ~ ~ ~ ~ ~
.. 7 er ,~ ~ ~ .
a~ ~r a~ 1
. - - ,,
c~ l ~ ~
~r ~ ~r ~ 1
- - - - -- - -
:~
-l ~l ~ l
~ ~ ~ ~ _ _I
~n a~~n
~rl ~ ~ rl
.~ rl ~ ~
~ O ~d ~ ~ O ~ ~ :',
5~ ~ ~ rl 5~ ~ 1
~d ~ ~ ~ , .
X bO ~ ~ O ~ .
O ~.C ~ O ~0.~ ~ , ~
zi ~ ~ ~ ,1 æ ~ ~ ~O ,,
S~ ~ ~ 5~ J~ i., .
a ~ ~ ~ ~ ~ ~ ~ ~ . ~
~o ~ ~ ~ 0~ O,a~ ~o ~ ~ : :.
,~ v ~ rl ~ ~ ~ ~ v ~
5, v ~ o v ~4 ~ ~ s~ v a~ o v bO ":
O ~ ~_1 0 ~ O C~ ~ ~ O ~ ~ O rl
c~,~ ~ 4 ~C ~ a w ~s ~ ~ ~:
., ~
.. .
t~ . ` . : -- --~ --~.. _ ~_ .. ___.. ~.. _ __~_ ~ _, _,,_ _ _
- ~ ' , . ' ':' : . , ' ''
. . ' ., ' ' '' . . , , ' ' , ' . .
' , ' ~ ' , . ~ ' :
~ 3~32
Post-emer ence herbicidal action ~contact herbicide)
_ g _ _ _ _
A considerable number (at Least 7) of weeds and of
cultivated plants, both monocotyledonous and dicotyledonous,
are sprayed after emergence (in the 4- to 6-leaf stage)
with an aqueous active~substance dispersion in dosage
amounts o 1, 1/2, 1/4 and 1/8 kg of active substance
per hectare, and they are then kept at 24 26C with
45-60% relative humidity. The test is evaluated lS days
after treatment, and the results are assessed according
to the same scale of ratings as used in the pre-emergence
~est.
The following plants are tested: wheat, soya bean and
sugar beet~ as weLl as the weeds Avena fatua, Lolium
perenne, Alopecurus myosuroides and Setaria italica
The results are summarised in the Table which follows.
, =~......................... . . . ;
,
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/~ 3~
.~ ,~
..
u~O ~
~ ,, ~ ~ ,, ,, ,, ~
__ ~ I U~
~ O a~ 1 a~ ~
~1 ~ l ~1 ~ ~ ~ O~ ~
_ _ _ __
r~ O a~ ~ O a~
~ ~ ~ c~
_ ~. _ _ _ _ . .'
. u~ I . a~ ~1
~o o ~ o
~ ~ ~1 ~ ~ ~ ~ 1
_ _ _
~ a~ I ~1 ~1 ~ ~ ~ ~
O r a~ ~ O ~ ,
. . -- . - :-
O ~ ~ ~ , ~,
,~ ~ 1 _1 ~ 1 : ~,
- - - - - -
. ~ a~ I .
O " O
,~ r~ _1 ~ ,
-- ~ - ~
) ~ 1 ~I Q ~ i.
r~l ao a~ 1 ~1 ~1 _I ~ ~ ~ ~I ~ l
_ . _ __ - O' '~,:
~r:l . ~c) ~ ~
h ~ O
~ O s.) ~, ~ ~
~ 5 Ei ~-l ~ C ~. ~
æ ~ 5. o ~ o~l~ s~
~ ~ ~ ~ ~ ~ ~ U ~ P
o ~ ~ u ~ o ~ ~ ~
8.~c ~ 3 1 83~ , o ~
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