Note: Descriptions are shown in the official language in which they were submitted.
;3~i
PROCE.SS FOR p-ALKENYL PHENOLS AND THEIR
SUBSEQUE.NT OXIDATION FORMING S~gTITUTED ~E;N-~LDE~IYnES
This invention relates to a novel process for
the preparation oE p-alkenyl phenols and the subsequent
preparation of the corresponding substituted
benzaldehydes. More particularly, this invention
relates to a novel process for the preparation of
1,1-hydrocarbyl-substituted-2-(3'-hydrocarby:L or
3',5'-dihydrocarbyl-4'-hydroxyphenyl)-ethene compounds
which are especially useful as intermediates in the
preparation of phenolic antioxidants for gasoline,
lubricants, plastics and rubber.
In accordance with one aspect of the invention,
an alkylated phenol having a replaceable hydrogen atom
at the 4- position and at least one hydrocarbyl
substituent ortho to the hydroxyl group is reacted with
an aliphatic aldehyde having two carbon atoms up to at
least 20 carbon atoms in the molecule and a secondary
amine to form the corresponding l,l-hydrocarbyl-
substituted-2-(3`-hydrocarbyl- or 3',5'-dihydro-carbyl-
4'-hydroxyphenyl)-ethene.
:.~ .
, i ,
L63V~
The invention cnn best be understood by the fol-
lowing detailed discussion oE the reactants and
conditions by which the p-aLkerlyL phenol products of
the present process are produced. The structure of
these products will, of course, be determined by the
nature of the starting phenolic and aldehyde reactants.
In general, any monohydroxybenzene compound
having a replaceable hydrogen atom on the ring carbon
atom para to the hydroxyl substituent and at least one
hydrocarbyl substituent ortho to the hydroxyl group, as
in the case of o-tert-butyl phenol, will serve as the
starting phenol. Since the products of the process are
principally useful as antioxidants or as intermediates
in the preparation of antioxidants, it is desirable
that the hydrocarbyl substituents be alkyl, aralkyl or
cycloalkyl groups sufficiently large to offer some
degree of hindrance to the phenolic group. It is
especially desirable that the hydrocarbyl substituent
be branched on the alpha-carbon atom and have at least
3 carbon atoms and, preferably, up to 8 carbon atoms;
although any number of carbon atoms, for example up to
about 40 carbon atoms, may be present in the hydrocarbyl
substituent as long as the substituents do not interfere
with the formation of the desired phenolic styrene.
Suitable o-hydrocarbyl phenols meeting these require-
ments include secondary alkyl-substituted phenols such
~Z~L63~3
as o-isopropyl phenol, o-sec-butyl phenol, o-sec-amyl
phenol and o-cyclohexyl phenol; while suitable tertiary
hydrocarbyl phenols are o-tert-butyl phenol and o-tert-
amyl phenol. Additionally, primary hydrocarbyl phenols,
such as o-benzylphenol, cun serve as starting phenols.
~ iost preEerred phenolic reactants in the process
oE this invention are dialkyl phenols wherein the phenol
has a replaceable hydrogen atom on the para ring carbon
atom and two hydrocarbyl substituents ortho to the
hydroxyl group. Preferably, at least one of the hydro-
carbyl substituents i9 branched on the alpha-carbon
atom and has from 3 to 8 carbon atoms. The substituents
need not both be the same hydrocarbyl radical. Specific
examples of particularly appropriate phenols are repre-
sented by 2,6-dimethyl phenol, 2,6-di-n-butyl phenol,
2,6-di-sec-butyl phenol, 2-isopropyl-6-methyl phenol,
2,6-diisop~opyl phenol, 2,6-di-tert-butyl phenol,
2,6-di-sec-octyl phenol, 2-methyl-6-cyclohexyl phenol,
2,6-di-(alpha-methylbenzyl)phenol, 2,6-dibenzyl phenol,
2-methyl-6-benzyl phenol and the like. A particularly
- preferred phenolic reactant for use in the present pro-
cess is 2,6-di-tert-butyl phenol.
Substituent groups other than those previously
listed such as aryl, chlorine, bromine, fluorine and
nitro groups and the like may be present at any of the
ring carbon atoms with the sole exception of the para
, . .. , . _ _,
ring carbon atom ln the aromatic phenolic reatant
provided they do not adverseLy affect the formation of
the desired l,l-hydrocarbyl-substituted-2-(3'-hydro-
carbyl or 3',5'-dihydrocarbyl-4'-hydroxyphenyl)ethene
product.
Preferred starting phenolic reactunts may be
described by the structure
OH
1 0 ~
wherein Rl and R2 are the same or different and are
hydrogen or hydrocarbyl radicals, preferably alkyl,
aralkyl or cycloalkyl radicals having up to at least 40
carbon atoms, and preferably from 3 to B carbon atoms,
at least one of which is branched on the alpha-carbon
atom with the provision that at least one of Rl or
R2 must be other than hydrogen.
Aldehydes which are applicable to the present
process are those aldehydes having a single aldehyde
radical of the general formula
H O
R3-C-C-H
R4
- 4 -
.~ :
.. . . . .
31)~
wherein R3 and R4 can be the same or different and
are selected Erom hydrogen or linear and branched alkyl
radicals having up to at least 40 carbon atoms, prefer-
ably up to 20 carbon atoms. Typical aLdehydes which mny
be used in the process of the invention include, by way
of example only, acetaldehyde, propionaldehyde,
butyraldehyde, isobutyraldehyde, caprylaldehyde,
decylaldehyde, tetradecylaldehyde, and the like.
Amine reactants which are applicable to the
present process are secondary amines; that is, deriva-
tives of ammonia having one hydrogen atom bonded to the
amino nitrogen atom and can be represented by the formula
R5-N-H
R6
wherein R5 and R6 are the same or different and are
linear or branched alkyl radicals having up to at least
40 carbon atoms. It is deemed, however, that secondary
amines containing nitrogen atoms in a ring structure
such as piperidine, pyrrolidine, morpholine and the like
also may be used. Preferred amines are dimethylamine,
diethylamine, dipropylamine, dibutylamine, disecondary
propyLamine, ethylmethylamine, metbylpropylamine,
methyl-n-butylamine, ethylisopropylamine and the like.
~2~63~
Under the reaction conditions, the a0ino reactant
lnitially combines with the phenolic and aldehyde reflc-
tants to yield a Mannich base type of intermediate which
upon further reaction spontaneously eliminates the amine
component to produce the olefinic Einal product. The
carbonyl carbon atom oE the aldehyde reactant, along
with the organic groups bonded to the carbonyl carbon
atom of the aldehyde, becomes bonded to the 4-carbon
atom of the phenol ring. Some aldol condensntion by-
product is produced during the reaction.
The 1,1-hydrocarbyl-substituted-2-(3'-hydrocarbyl
or 3',5'-dihydrocarbyl-4'-hydroxyphenyl)etherle products
of the process can be represented as those compounds
having the general formula:
Rl
H0 ~ CH - C
R2
wherein Rl and R2 are the same or different and are
hydrogen or hydrocarbyl radicals selected from the group
consisting of alkyl, aralkyl or cycloalkyl radicals
having up to at least 40 carbon atoms with the provision
that at least one of the Rl or R2 radicals must be
~L63~
other than hydrogen and R3 and R4 are the same or
different and are hydrogen or linear or branched alkyl
radlcals having up to at least 20 carbon atoms in the
molecule with the provision that one of R3 or R4
must be other than hydrogen.
The process of the invention is carriecl out by
reacting the phenolic starting material with at least
one molar equivalent of aldehyde and at least û.l. molar
equi~alent oE amine. It is preEerred, however, that
the reaction be conductecl witl- a molar excess of both
aldehyde and amine reactants with respect to the start-
ing phenol. A preerred range of aldehyde to phenolic
reactant is from 1 to 10 moles of aldehyde per mole of
phenol. A preferred molar range of amine reactant to
phenolic reactant is from 0.1 to 10 moles of amine per
mole of phenol.
The reaction can be conducted at a temperature
from S0C. to 250C. While lower temperatures can
be used, the reaction rates are generally too low to be
of interes~. Temperatures above 250C. can be used,
but excessive decomposition of the reaction
components can occur. The preferred reaction tempera-
tures are from 50C. to 200C.
The reaction can be conducted at atmospheric
pressure or at higher pressures, with moderate pressures
up to about 300 psig being preferred.
~L2~LG3~
The use of a solvent for the reaction mixture is
noL generally required, though, iE desired, a solvent
which is inert un(ler the reaction conditions, i.e.,
those solvents which do not enter lnto the reflction,
may be added to the reaction vessel. Useful solvents
comprise aprotic solvents which include ethers such as
diethyl ether, dibutyl ether, I-ethoxyhexane, tetra-
hydroeuran, 1,4-dioxane, 1,3-dioxolane, diglyme,
1,2-diethoxyethane and tertiary amines such as pyridine,
N-ethylpiperidine, triethylamine, tributylamine, N,N-di-
phenyl-N-methyl amine, N,N-dimethylalanine, etc. Espe-
cially useful solvents are dipolar aprotic solvents
such as dimethyl sulfoxide, N,N-dimetbylformamide,
N,N-dimethylace~amide, dimethyl suleone, tetramethylene
sulfone, N-methylpyrrolidinone, acetonitrile and like
lS materials. Other solvents which are inert under th,e
reaction conditions may be used: for example, low boil-
ing hydrocarbons, halogenated hydrocarbons, examples Oe
which are benzene, toluene, tetrachlornethane, the
chlorinated benzenes, the chlorinated toluenes, etc.
Especially preferred solvents are lower alkanols having
up to about 6 carbon atoms. These include methanol,
etbanol, n-propanol, isopropyl alcohol, n-butanol, sec-
butyl alcohol, tert-butyl alcohol, n-pentanol, isopentyl
alcohol, n-hexanol and isohexyl alcohol.
.. _. . _.. . . . . ., . . .. . . , . __ _ _.. _ .
~l2~ 3~
The amount of solvent can be expressed fl6 a
volume rat;o of solvent to phenollc reactant. Suitable
volume ratior~ of solvent to phenollc reactant can be
from 0/1 to 500/1 and preferably from 1/1 to 300/l.
The mode oE addition in the process is not par-
ticularly critical. Accordingly, it is convenient to
add the phenolic reactant to a mixture of the other
materials, add the aldehyde to a mixture of the other
materials, add the amine reactant to a mixture of the
other materials, add the reactants to a mixture of
the amine and solvent, introduce all ingredients simul-
taneously into the reaction zone, or the like.
Ii a gaseous amine is selected for use in the
process, the reaction is carried out by passing the
amine in its gaseous state through the reaction mixture
in a reaction vessel with agitation to olutain intimate
contact of the reactants. To ensure that the a~ount of
amine does not exceed that amount required, as
hereinabove shown, the amount of amine in contact with
the other reactants can be controlled by limiting the
flow of amine through or into the reaction vessel.
The process should be carried out for the time
sufficient to convert substantially all of the phenolic
reactant to the corresponding p-alkenyl phenol. The
length of time for optimum yield will depend primarily
~63~13
upon the reaction temperature and l:he particular aol-
vent, if any, used in the renction. In gener~l, excel-
lent yislda oE p-alkenyl phenol are obtalned in from
about two to Eorty-eight hours.
Although not required, the process can be con-
ducted in a substantially anhydrous reaction sysLem,
and accordingly, the components oE the reaction system
are brought together and maintained under a substan-
tially dry, inert atmosphere. ~y "substantially
anhydrou9" is meant a reaction system wherein the total
amount of water present is no more tban about 5 percent
by weight, based on the reaction mixture. When the
amount oE water in the system exceeds this, both reac-
tion rate and yield of product decrease.
The process may readily be conducted in a batch-
wise, semi-batch or continuous manner and in conven-
tional equipment.
The product p-alkenyl phenol is easily separated
from the reaction mixture by such means as distillation,
extraction, crystallization and other methods obvious
to those skilled in the chemical processing art.
The practice of this aspect of the invention
will be still further apparent by the Eollowing
illustrative examples.
- 10 -
i3~
Example I
Preparation oE 1 1-Dimethyl-2-(3',5'-Di-t-ButYl-
hr-llydroxyphenyl)E-hene
2,6-di-tertiary-butyl phenol (4.1 g; 20 mmol),
isobutyraldehyde (3 ml; 33 mmol), dimethylamine (1.5 g;
34 mmol) dissolved in isopropanol (7.5 g) were charged
to a 100 ml glass vessel and reEluxed at ambient pres-
sure under nitrogen for 48 hours. The resultant reac-
tion mixture was allowed to cool to ambient tempetature
and concentrated to a yellow oil which was recrystal-
lized Erom a mixture oE ethanol and water (90:10) to
give yellow crystals (3.7 g; 71% yield) oE l,l-dimethyl-
2-(3',5'-di-t-butyl-~ hydroxypheny])ethene as charac-
terized by VPC, mass spectrocopy and NMR.
ln a manner similar to ExampLe I above, a number
of experiments were carried out varying the temperature,
reaction time, pressure, reactants and ratio oE reac-
tants. The results were analyzed by vapor phase chromo-
tography with internal standards and are shown in the
Table below.
3~
1~ O O r~ ~ ~ O
Z U ~ ~ , o~
tP
~ U~ o. ~
. ~ ~ N ~ ~1 ~ Ul ~ N ~1
'~ S
_ e C C C c c C c
S. ~ ~3 E U ) R ~ e ~ ~ Ul ~7
-- K ~ ~ ~ ~ ~ a o ~ ~ a u~
O ~ o~ O a~ ,n
,~
n-
ZO ~ ~ ~ C O ~ i s ~ ~ ~"
a~ u~ u~ o
_ H H ~ E~ '¢ H Z ~ :IC a ~ Z
N ~i Ul
~ C ~
v .,. ~ u~ ~ o
.~1 . _
~ 1 ~
c3 5~'
OO ~ E ~ o o o 0 l~ ~ ~ ~ N
~Vl ~ E
~:1_~ .
I ~1 O o o O o U~ "~ o ~ ~ ~ o
_ . '
¦ N "~ 0 ~ O --I 1`1 ~') .r
~; Z ~
~ dP
E ¦ '`I ' C ¦ N
-, ~ C ~ ~ C
~P~ P~ I ~
~0 -~ ~
3 o~ ~:
N ~ _ N ~ E
~ I ~ I
zl ~ t~;zl ,,
_ 13 - ;
-` ~L2~3
.,.1 ~ 1~
~- r~ ~
OP ~I dP
E
'~ S ~D '~
o/~
~4 1
Cl Eo~ 0
a~ '~: '',~
~OD ~ ~
C' ~ ~ o ~--e~
n i ~ I
c 1 ~; zl
:
- 14 -
;3~
In another aspect of this invention, the
1,1-hydrocarbyl-substituted-2-~3'-hydrocarbyl- or
3',5'-dihydrocarbyl-4'-hydroxyphenyl)ethene products
produced by the process of the present invention can be
directly oxidized to the corresponding 3-hydrocarbyl-4-
hydroxybenzaldehyde or 3,5-dihydrocarbyl-4-hydroxyben-
zaldehyde by contacting with good agitation the afore-
mentioned l,l-hydrocarbyl-substituted-2-(3'-hydrocarbyl-
or 3',5'-dihydrocarbyl-4'-hydroxyphenyl)ethene with at
least a stoichiometric amount o~ oxygen in the presence
of a small catalytic quantity of a catalyst selected
~rom the group consisting of a Lewis acid, an alkali
metal salt of a weak acid or an alkaline mearth metal
salt of a weak acid, an alkali metal hydroxide or an
alkaline earth metal hydroxide, or amine bases until a
reaction product containig a substantial amount of the
corresponding 3-hydrocarbyl-4-hydroxybenzaldehyde or
3,5-dihydrocarbyl-4-hydroxybenzaldehyde is formed.
Alkylated hydroxyphenyl aldehydes and methods
for their preparation are known. For example, U.S.
4,009,210 discloses a method for preparing 3,5-di-tert-
butyl-4-hydroxybenzaldehyde, a chemical intermediate
for the manufacture of pesticides of the benzylidene-
malononitrile type, by reacting 2,6-di-tert-butylphenol
with bexamethylenetetramine or a combination of formal-
dehyde and ammonium acetate in aqueous acetic acid
reaction medium.
.... .. ~
SaZ~L63~)8
A new process Eor the synthesis o~ 3-hydrocalbyl-
4-hydroxybenzaldehydes or 3,5-dihydrocarbyl-4-hydroxy-
benzflLdehydes has now been discovered in which these
materials can be prepared in A simple and straight-
S Eorward manner. In this new process, p-alkenyl pbenols,
in particular l,l-hydrocarbyl-substituted-2-(3'-hydro-
carbyl- or 3',5'-dihydrocarbyl-4'-hydroxyphenyl)ethenes
are contacted with oxygen in the presence of a catalyst
selected from a Lewis acid, an alkali metal hydroxide
or arl alkaline earth metal hydroxide, an alkali metal
oE a weak acid or an alkaline earth metal salt oE a
weak acid or an amine base. In accordance with the pro-
cess, cleavage of the oleEinic bond located at the
4-position oE the phenyl ring oE the p-alkenyl phenol
reactant takes place by a radical process whereby the
desired alkylated hydroxyphenyl aldehyde product is
produced.
The 1,l-hydrocarbyl-substituted-2-(3'-hydro-
carbyl- or 3',5'-dihydrocarbyl-4'-hydroxyphenyl)ethenes
which are oxidized according to the aEorementioned
process are those compounds described and prepared here-
inabove.
The process is readily conducted by placing the
1,1-hydrocarbyl-substituted-2-(3'-hydrocarbyl- or 3',5'-
dihydrocarbyl-4'-hydroxyphenyl)ethene and other reaction
mixture components in a reaction vessel having agitation
- 16 -
.. ...... , , . _ .. . .. . _ _ _
. .
" ~2~Li3~
means, or can be advantageously carrLed out, for exam-
ple, by passing the l,l-hydrocarbyl-substitutecl-2-(3'-
hydrocarbyl- or 3',5'-dihydrocarbyl-4'-hydroxyphenyl)-
ethene through appropriate reaction tubes and slmply
contacting the same with oxygen or an OKygen containing
gas and catalyst. The oxidation reaction should be
carried out with agitation and preEerably with vigorous
agitation or using other means that affotd intimate
contact between the oxygen containing gas and the reac-
tion mixture.
An essential component of the reaction mixtureis a catalytic amount of a catalyst, the suitable cata-
lysts being selected from the group consisting of alkali
metal hydroxides, alkali metal salts of a weak acid,
alkaline earth metal hydroxides, alkaline earth metal
salts of a weak acid, amine bases, mixtures oE the same
and Lewis acid catalysts. Illustrative of suitable
catalysts are sodium hydroxide, potassium hydroxide,
barium hydroxide, rubidium hydroxide, cesium hydroxide,
potassLum carbonate, sodium carbonate, cesium carbonate,
rubidium carbonate, potassium sulfite, sodium borate,
potassium acetate, diazabicyclononane, pyridine, tetra-
methylguanidine, 1,4-diazabicyclo-(2,2,2)-octane,
FeC13, LF3, ZnC12, TiC14, HF, H2S04, H3P04, SnC12,
SnC14, and CuC12. Copper chloride and ferric
chloride are preferred catalysts.
- 17 -
:. ' '
.
3~
The amount o~ catalyst used is not narrowly
critical but only a small amount is suf~icient to pro-
mote cleavage of the olefinic bond at the 4- position
of the l,l-hydrocarbyl-substituted-2-(3'-hydrocarbyl or
3',5'-dihydrocarbyl-4'-hydroxyphenyl)ethene reactant.
In general, the amount used can be as little as 0.1
weight percent through amounts up to 1 weight percent,
based on the ~seight of p-alkenyl phenol reactant, and
evcn greater amounts of catalyst may be used if desired.
In the practice of the invention, the amount of
oxygen employed relative to the l,l-hydrocarbyl-substi-
tuted-2-(3'-bydrocarbyl- or 3',5'-dihydrocarbyl-4'-
hydroxyphenyl)ethene starting reactant is not critical.
In general, only an amount of oxygen required for the
direct oxidative cleavage of the p-alkenyl phenol to
the corresponding benzaldehyde should be used. For
best results, however, it is preferable that at least a
stoichiometric amount of oxygen or an amount greater
than that stoichiometric required is used.
The reaction is conducted, for example, by pas-
sing oxygen, and preferably an oxygen containing gas
such as air, through the reaction mixture in a reaction
vessel with agitation to obtain intimate contact of the
reactants. Typically, the reaction is conducted at
atmospheric pressure, however, higher pressures up to
about 200 psig may be used, if desired. The amount of
- 18 -
~lZ3L~3~
oxygen reacting with the p-alkenyl phenol reactant can
be, in general, easily controlled by llmiting the flow
oE gas through or into the reaction zone.
The reaction can be conducted at mildly elevated
temperatures of, for example, from 25C. up to higher
temperatures of 250C. and preferably at fl
temperature that ranges from 50C. up to 150C.
Reflux temperature at atmospheric pressure i8 effective
and preferred.
The use of a solvent for the reaction mixture is
not generally required, though, if desired, a solvent
which is inert under the reaction conditions, i.e.,
those solvents which do not enter into the reaction,
may be added to the reaction vessel. Especially pre-
ferred golvents are dipolar aprotic solvents such as
dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethyl-
acetamide, dimethyl sulfone, tetramethylene sulfone,
N-methylpyrrolidinone, acetonitrile and like
materials, Other solvents which are inert under the
reaction conditions may be used: for example, tertiary
amines such as pyridine, N-ethylpiperidine, triethyl-
amine, trlbutylamine, N,N-diphenyl-N-methylamine,
N,N-dimethylalanine; low boiling hydrocarbons and
halogenated hydrocarbons, examples of which are
benzene, toluene, tetrachloroethane, the chlorinated
benzenes, the chlorinated toluenes, etc, and lower
- 19 -
3~
alkano1s having up to about 6 carbon atoms which in-
clude methano1, ethanol, n-propanol, isopropyl alcohol,
n-butanol, sec-butyl alcohol, tert-butyl alcohol,
n-pentanol, isopentyl alcohol, n-hexanol and isohexyl
alcohol.
The amount of solvent can be expressed as a
volume ratio oE solvent to alkenyl phenol reactant.
Suitable volume ratios of solven~ to alkenyl phenolic
reactant can be from 0/1 to 500/1 and preferably from
1/1 to 300/1.
The process should be carried out for a time
sufficient to convert substantially all of the para-
alkenyl phenol reactant to the corresponding alkylated
hydroxyphenyl aldehyde. In general, the length of time
for optimum yield depends primarily on the reaction
temperature, the type and amount of catalyst and the
particular solvent used in the reaction. In general,
excellent yields of product are obtained in Erom 1.5 to
6 hours.
If desired, the process alternatively may be
cortducted to continuously produce the benzaldehyde
products oE the invention. A suitable continuous reac-
tor generally consisting of a length of vertically
mounted reactor tubing having heating or cooling means
surrounding it may be employed.
- 20 -
The product aldehyde can be easily separated
~rom the reactant mixture by such means as distillatlon,
recrystallizution and other methods obvious to those
skilLed in the chemical processing art.
The following examples serve to illustrate the
formation of alkylated hydroxyphenyl aldehydes from
para-alkenyl phenols.
Example 19
Preparation of 2,6-Di-t-Butyl-4-HydroxYhenzaldehyde
A lûO ml glass reaction vessel was charged with
1.1 g (4.3 mmols) 1,1-dimethyl-2-(3',5'-di-t-butyl-4'-
hydroxyphenyl)-ethene. Ferric chloride hexahydrate
(0.03 g; 0.12 mo)ols) was suspended in approximately 6 g
of N,N-dimethylformamide and added to the reaction ves-
15 sel. Oxygen (17.7 g; 550 mmols) was slowly introduced
into the solution in the reactor which gradua]ly dar-
kened the solution. After 1.75 hours, the black reac-
tion mixture was filtered through a silica gal pad and
the filtrate was concentrated to give a black semi-solid
20 product (0.75 g; 74~ yield) of 2,6-di-t-butyl-4-hydroxy-
benzaldehyde as identified by gas chromotography and
thin layer chromotography.
In a manner similar to Example 19 above, a
number of experiments were carried out varying the
temperature, reaction time, solvent and type of
catalyst. The results are shown in the Table below.
- 21 -
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a, I o ~ ~D O U~
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d~
In
o~Ul
U~
,. . .
X X X X
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a) E~ o 1
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N '~-: o
O ~o
~ ~ o
H . o U
., :' ~ ,.,E3,.1 --~ o
~¢, m o~ ~ ~ ~ ~ I s
~c> O S o o
¦ H ~ H H E- ~,
O X
.~ V S
E
~4 v E3 --' V
C~ ~ , n :.,
~ V ~
~ J o ~: . ~ :
æ C~ 1~ æ æ ,
_ r
V I S
o _~ ~1 111 _, v
P~ 3 ~ 'r o ~_~ E
I
~ ol o ~
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