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Патент USA US2404300

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Patented July 16, 1946
2,404,300
v
@PATENT
OFFICE.‘ ,
‘ UNITED JISTATESF
7 Lucas
Kyrides', Webster Groves, and Ferdinand - ‘
B. Zienty, St. Louis,_Mo., assignors to Monsanto,
' Chemical Company, St. Louis, Mo., a corpora
‘a
tion of Delaware
No'Drawingl' Application March 22, 1944,
-
Serial No. 527,074 '
7 Claims.
1
The present invention relates to the productionv
thesis of the imidazole derivative or immediately
thereafter and before the productis isolated from,
cants which are substituted imidazole compounds,
and comprises the method of producing these
compounds as well as'the new products them
'
.
According to the present invention, generally
stated, new products which are of outstanding
value as active agents against micro-organisms
the
The
reaction
products
mixture.
of the present‘invention
. a
, have _ also
5 been found to possess utility as insecticides and
toxicants for insecticide compositions,_ such asv
sprays and powders in which the compounds are
blended with suitable wetting agents, ?llers, sol
vents,‘ adhesives, coating agents, _ repellents, and
are made by preparing substituted imidazoles of 10
the type represented by the formula:
i
(Cl. 260-—309)
of new bactericidal agents and insecticide toxi
selves.
‘
‘
‘
other ingredients employed in compouhdingin- V t
secticides.
.
-
-
I
The products of the present invention maybe
prepared by reacting ethylene \diamine, with a
molecular equivalent or less of an ‘acylating agent.
15 comprising an altiphatic monocarboxylic acid.‘
having as its alkyl residue one ofv the radicals
described hereinbefore in the de?nition, of R1
in which R represents an acyclic hydrocarbon‘
radical having froml to 5 carbon atoms in its
with respect to the formula. The acid thus em‘
ployedwill be composed of'a straight'chain alkyl
residue of the proper chain length together with
structure and R1 represents an acyclic hydrocar
a carboxylic acid group, thecarbon atom of ‘which,
vbon radicalhaving fromlO to 16 carbon ‘atoms
is not included in the contemplation of the chain
in its structure. The acyclic hydrocarbon radi
length hereinbefore described. Inthe place of the
cal represented by R may be a straight chain alkyl
acid5thealkyl ester, such as the butyl ester; or:
radical such as the methyl, ethyl, propyl, butyl
and amyl radicals, or a branched chain alkyl radi .26 desirably the methyl or ethyl ester, may be CHI-f
cal such as the isopropyl, tertiary butyl and iso ' ” ployed, or the acyl halide such as the acyluchlo
ride, or the acid anhydride. The resulting mono
amyl radicals. Likewise R may be an alkenyl
acyl amino derivatives is then'condensed. with
radical having from 1 to 5 carbon atoms in its
the aid of va suitable mild dehydrating agent,
straight or branched chain structure, for ex
ample, the propenyl, butenyl and isobutenyl radi
, such as; powdered calcium oxide, to form the 2
cals. The acyclic hydrocarbon radical repre
sented by R1 may be composed of a straight chain
’ n-alky1_-4,5-dihydroimidazole.' ' The
derivative
thus prepared is then reacted with an alkylating
agent having as its alkyl or alkenyl residue one
alkyl radical such as the decyl, undecyl, dodecyl,
of the residues described hereinbefore in the def
tridecyl, tetradecyl, pentadecyl and hexadecyl
radicals, or a straight chain alkenyl radical, such ’35- inition of R with respect to the formula. The
alkylating agent may be a mineral acid ester such
as the decenyl, undecenyl, dodecenyl, tridecenyl,
tetradecenyl, pentadecenyl and hexadecenyl rad
as an alkyl sulfate or alkenyl sulfate. Also, the
alkylating agent may be an alkyl halide or an
icals in which one or more double bonds may be
located in various positions in the chain. The
alkenyl halide. The “derivative thus prepared is r
water-soluble salts of these compounds may be :
prepared and are also valuable therapeutic agents
and insecticide toxicants. For example, thehy
drochlorides, hydrobromides and acetates and’
other salts may be employed.
,
45
. The new products andrtheir water-lsoluble salts
have been found to be unusually effective against
micro-organisms such as streptococcus in vitro
and in vivo. The organic and inorganic acid
salts may be prepared ‘by dissolving the products
to
in an aqueous solution containing the‘stoichio
metrical equivalent’ of. a suitable acid," such as
then dehydrogenated with the aid of a suitable
dehydrogenation catalyst, such asnickel, to form'
the l-alkyl '(or 'alkenyl)'-2—alkyl (or alkenyl‘)
.imidazole.
,
~
' '
’
In carrying out the preparation of .the N-acyl
ethylene diamine, it is‘desirableto employ an
hydrous ethylene diamine. However, ethylenedi
amine that is not substantially anhydrous may g
be employed. The anhydrous material facilitates
the attainment of somewhat higher yields.
The following examples illustrate ‘the process of
the present invention and the compounds result
hydrochloric, hydrobromic, acetic acids, and the
ing, therefrom. These examples are tofbe' con‘
like, and the solution may be employed. Also,
strued
as merely illustrativeand not as limiting
the acid salts may be prepared during the syn; 5.5 the scope
of the‘ present invention.
"
‘
.
2,404,300
'3
EXAMPLE I.
150 cc. of water and approximately 150 cc. of bu
tyl alcohol was added to the reaction mixture
1 -methyl-Z-n-undecyZ-imidazole
slowly with agitation. The mixture was then
'cfH—N+oHa
CH
C-CH2(CH2)~0~ CH3,
\ ¢
4
grams of 50% sodium hydroxide in approximately
.
5 agitated for 1 hour at roomtemperature. The
' butyl alcohol layer was separatedand thereafter
‘
distilled to remove butyl alcohol and Water. The
residue was then distilled at reducedpressure to
A mixture of 1'11 grams (0.75 moles) of ethyl .
I laurate and 135 grams (2.25 moles) of anhydrous I
recover the product. The B. P. of the product
12 hours. The reaction mixture was transferredv ‘was
145 180
mm’Was
The
meld of ploduct
was v‘770.3%
‘andC'/5/2
the assay
substantially-100%.
to a stilland the alcohol and'excess ethylene di
The product was identi?ed as ,2-n-amyl-2-n-‘un
ethylene-diamine was re?uxed at 110-112“, C. for 3.
;
o
1
-
.
amine were removed by distillation. The’ yield V
decyl-dihydroimidazole. ‘ A mixture of 4.2» grams
of crude N-acylated ethylene diamine was/1'72‘ ‘ vof nickel catalyst, prepared according ‘to the
method of Example I, and 37.1 grams of l-amyl
grams.
A mixture of 162 grams of the crude N-'acyl= is 2en-undecyl-4,5-dihydroimidazole was heated with
ethylene diamine and‘ 187 grams of powdered1 . agitation to 212-246" C. vuntil hydrogen was no
calcium oxide was heated with stirring at 225°
longer evolved. The reaction mixture was then
C(for 36 hours. The reaction mixture was cooled
distilled. The fraction distilling at 18§~210°/5
and extracted 3 times with about 350 cc. of_ al- 20 mm. was recovered. The product was l-amyl
cohol at room temperature. The alcohol was re
Z-n-undecyl-imidazole.
Yield 76.6%.
. 1
.
moved by distillation and ‘the product "was dis
tilled‘by reduced pressure. 'The'boilirig point‘of
‘
'
EXAMPLE
III
‘
1 -methyl-2-n-decyZ-imidazole
the ‘product was ISO-189° C./10 mm. ‘The M. P.’
of. the product was >87
uct was 98.5 grams.
'
2's
CH—N-—CHs
7
Thelproduct was" identi?ed as 2-undecyl-4,5-di
hydroimidazole. To 56.5‘ grams of 2-undecyl
4,5-dihydroimidazole was added 31.7 grams of
- . A mixture of 160.5 grams of the ethyl ester
dimethyl sulfate‘ over a period of 32 minutes. 30 of n-undecanoic acid and'135grams of anhydrous
ethylene diamine was reacted according to the
The temperatureof the reaction mixture'was
method of Example I. The resulting N-un
maintained atmabout 85° 'C. To the reaction mix
decanoyl ethylene diamine was condensed with
ture was added’approximately 150 cc. of water,‘
anhydrous calcium oxide according to the meth
and the mixture was stirred until the solid ma
terial had dissolved. A solution of 20 grams of‘ 35 od of Example I. The resulting 2-n-decyl-4,5
50% sodium hydroxide and approximately 15000.3
dihydroimidazole was then reacted with dimeth
yl sulfate according to the method of Example I
of butylalcohol was added to the mixture with‘
agitation. aThamixture was then filtered, and‘
to form 1,-methyl-2-n-decyl-4,5-dihydroimida
the butyl alcohol layer'of' the ?ltrate was dis
zole.
This material may then be dehydrogenated
The
tilled to‘ remove butyl alcohol _. and water. _The 40
'
according to the method of Example I.
residue was'then distilled at reduced pressure~ to:
recover the product. The B. P. of the product
product is 1-methy1-2-n-decyl-imidazole.
was 16'7—1'72° -C./6 mm. The yield of product was
38%‘ and the assay was 96.2%. The product was
1 -methyl-Z-n-dodecyZ-imidazole‘
EXAMPLE IV
V
identi?ed ‘as g1-methyl;2¢n-undecyle4,5-dihydro
cH-m-om
imidazolea
‘
‘
i
I
_
CH
I
‘ For the ‘dehydrogenation of 1-n-dodecyl-2
methyl-4,5-dihydroimidazole, . a
dam-(croutons
‘
'
‘
N
nickel ‘ catalyst
was ‘prepared by heating nickel formate in a
A mixture of 162 grams of the methyl ester of
mineral oil until decomposition of the formate 50 tridecanoic acid was reacted with 135 grams of
occurred. The nickel catalyst may be prepared
anhydrous ethylene diamine according to the
method of Example I. The resulting N-tridec
' by other; methods, for example. the method dis
closed in‘U. S. Patent 1,378,736,-issued May v1'7,
anoyl ethylene diamine was condensed with an
be employed. A mixture of 3.1 grams of the cat
imidazole. This product was then reacted with
dimethyl sulfate according to the method of Ex
1921, ‘to Ellis. Other suitable dehydrogenation
hydrous calcium oxide according. to the method
catalysts, such as Raney' nickel catalysts, may 55 of Example ‘I to form 2-n-dodecyl-4,5-dihydro
alyst thus prepared and 30.9 grams .of l-methyl
'2-n-undecyl-4,5 -.dihydroimidazole was heated
with agitation to 226° C.-246° C. until hydrogen
ample I to form 1-methyl-2-n-dodecyl-4,5~dihy
.droimidazole. This material may then be dehy
drogenated according to the‘method of Example
I. The product'is l-methyl-2-n-dodecyl-imida
was no longer‘ evolved. The reaction mixture
was then distilled; B. P. 166-203°/5 mm. The
product’ was
1-methy1-2-n-undecyl - imidazole.
Yield 85.3%.
.
v
zole.
'
EXAMPLE V
v
EXAMPLEII
. ‘ 1 -n-amyl-j2 -n-undecyZ-imidazole
'
05
oH--_N—o11l-‘(oHl)‘a-c11'3
on
'\
o-onMoHm-om
¢
‘
~
_
"
N
This compound may be'prepared by reacting
To 84.9 grams ‘of, 2-n-undecyl-4,5-dihydroim 70 2-n-dodecyl-4,5-dihydroimidazole, prepared ac
idazole heated to 140-150° was added dropwise
cording to the methodof Example IV, with di
21.7.. grams of. n-amyl chloride. The tempera
ethyl sulfate according, tov themethod of Ex
ture of; the reaction mixture was held at 147-154“
ample, I using the stoichiometrical proportions
C. for a total of 16 hours.v Thereaction mixture
desired therein. This material may then be de- '
was then cooled to 60° C. A solution of 17.1
2,404,300
5 .
hydrogenated according to‘the method of Ex
ample I. The product is 1-ethyl-2-n-dodecyl
imidazole.
A mixture of 270 grams ('1 mole) of crude N-n-'
tetradecanoyl ethylene diamine and 280 grams (5'
moles) of powdered calcium oxide was heated
With agitation at 225-230“ C. for.v 36 hours. The
-
EXAMPLE VI
1 -isop1opyZ-2 -n-dodeeyl-imidazole
/CHs
"
5 mixture was then cooled and extracted with al-,
cohol. The alcohol layer was separated and the
solvent was removed therefrom by evaporation,
'
leaving 130 grams of crude amine base. The base
foH5~N~on
'“
Y
.CH:
'
.
CH
,
'
was distilled, yielding 70‘ grams of a paleyellow,
crystalline, waxy solid material identified as 2-n
,
10
'C—-CH;.(CH2)10.CH3
tridecyl imidazoline -(2-n-tridecyl-4,5-dihydro
\N% .
imidazole) ; M. P., 87-88° C. with slight previous
This compound may be ‘prepared by reacting
softening. rI'his productmay then be reacted with
2-n—dodecyl-4,5-dihydroimidazole, prepared ac- it
dimethyl sulfate according to the method of Ex
ample I, using the stoichiometrical proportions
cording to‘ the method of Example IV, with iso
propyl chloride according to the method of .Ex
described therein.
ample II using the stoichiometrical proportions ‘
methyl-2~n-tridecyl-4,5-dihydroimidazole. This
The resulting product is 1
material may then be dehydrogenated according
described therein. This material may "then be
to the method of Example I. The product is 1
dehydrogenated accordingto the'method of Ex
.
ample I. The product is_l-isopropyl-2-n-dodecyl- 20 methyl-Z-n-tridecyl-imidazole.
In place of calicum oxide, other suitable de
imidazole.
/
-
EXAMPLE VII
hydrating agents, such as other alkaline-earth
‘
oxides, for example, barium oxide, and other mild
dehydrating agents, may be employed. However,
1 -allyl-Z-n-dodecyl-imidazole
CH—N—~CH1.CH=CH1'
(")H
\
calcium oxide is the desired agent because of its
—CH:.(CH2)lu-CHI
¢
‘
cheapness and e?iciency.
'
i
EXAMPLE X
‘ This compound may be prepared by reacting
1 -methy_l-2-n-tetradecyZ-imidazole
2-n-dodecyl-4,5-dihydroimidamle ‘prepared ac-.
cording to the method of Example IV, with allyl
bromide according to the method of Example II,
using the stoichiometrical proportions described
therein. This material may'then be'dehydro
This compound may be prepared by reacting a
mixture of 183 grams of the methyl ester of pen
tadecanoic acid and 135 grams of ethylene d1-'
amine according to the method of Example I.
genated according to the method of Example I. 35,
The product is substantially 1-ally1-2-n-dodecy1
imidazole,
'
EXAMPLE VIII
The resulting N-pentadecanoyl ethylene diamine
1 -methaZZyl-2-n-dodecyZ-imidazole
was condensed with anhydrous calcium oxide ac
cording to the method of Example I to form 2-n
tetrad'ecyl-4,5-dihydroimidazole._ The product
was reacted with dimethyl sulfate according to the
method ofv Example I, using the stoichiometrical
proportions described therein. The resulting
product was 1.-methyl-2-n-tetradecyl-4,5-dihy
This compound may be prepared by reacting
2-n-dodecyl-4,5-dihydroirnidazole, prepared ac
cording to the methpd of Example IV, with meth
allyl chloride according to the method'of Ex
ample II, using the stoichiometrical proportions
described therein. This material may then be
dehydrogenated according to the method of Exa
ample I. The product is substantially I-meth
allyl—2-n-dodecyl imidazole.
EXAMPLE
.
IX
droimidazole. This material may then be dehy
drogenated according to the method of Example
I. The product is 1-methyl-2-n-tetradecyl
_ imidazole.
It is desirable to use anhydrous ethylene di
amine in the process described in this and other
examples to facilitate the attainment of higher
yields. VHowever, ethylene diamine that is not
substantially anhydrous may be employed.
'
'
ExAMPLa E
'
1-methyl-zan-pentadecyl-imidazole .
1-meth.yl-Z-n-tridecyl-imidazole
CH——N—-CHa
CH
\N
’
—CHi-(CH2)11.CH3
I to "
A mixture of 426 grams. (1.5 moles) of n-butyl
myristate and 270 grams (4.5 moles) of anhy
drous ethylene diamine was re?uxed at 115° C. for
10 hours. The excess ethylene diamine and the
butanol resulting ‘from the acylation were then
distilled off, the distillation‘being'completed at
a reduced pressure of 10 mm. . The crude prod
uct remaining in the still weighed 377 grams and
melted at about ‘122°’ C. with extensive previous
softening. 'After recrystallization from alcohol,
?lH—-N-0Hi
on éo-ormomm-ong
N
v
I
_
.
A mixture of 193.5 grams of methyl palmitate
was reacted with 135 grams of anhydrous ethylene
diamine according to the method‘of Example I.
The resulting N -palmitoyl ;ethylene_diamine was
condensed with anhydrous calcium oxide accord
ing to the method of Example I to form 2-n
pentadecyl-4,5-dihydroimidazole. This product
0 was reacted with dimethyl sulfate according to
the method of Example I to form l-m'e'thyl-z-n
pentadecyl-4,5-dihydroimidazole.‘ v This material
may then be dehydrogenated' according to'the
the M. P. was 150-1520 C. The product was found
method of Example I. The product is' l-methy'li‘
to be appreciably soluble in benzene.
~ 75 Z-n-pentadecyl-imidazole.‘
‘ '
‘
\
"
2,404,399
~
8
1 LethgZ-Z -undecyI-imidazole
("3H-—.N—C1H5
o'—oHz.(oH5)».0H@'
CH
N
Fifty grams of 2-undecyl44,5-dihydroimidazole
'
' This compound may be prepared by reacting a
was melted and held at 70-80° C. ‘The melt was
mixture- of 204 grams of methyl margarate and 10 agitated while 19 cc. (34.4 grams) of ‘diethyl
135 grams of anhydrous ethylene diamine ac
sulfate was added slowly and simultaneously with
cording to the method of Example'I. The re
8.9 grams of sodium hydroxide in sufficient water
sulting N-heptadecanoyl ethylene diamine is con
to make 20cc. After all the diethyl sulfate had
densed‘ with anhydrous calcium oxide according
been added, the reaction mixture Was heated for
to the method of Example I to form 2-n-hexa
2 hours at 80° C. and thereaftercooled approxi- '
15
decyl-4,5-dihydroimidazole. This product is re
'mately to room temperature. To this reaction
acted with dimethyl sulfate according to the .
mixture was added 100 cc. of butanol and 40
method of Example I to form 1-methyl-2-n-hexa
grams of 50% caustic soda solution. The mix
decyl-4,5-dihydroimidazole. This material may
ture was stirred for 11/2 hours. The butanol lay
then’be dehydrogenated according to the method
er was separated fromrthe mixture and’ washed
20
of Example I. The product isl-methyl-Z-n-hex
twice with 50 cc. of water. The washed material
adecyl-imidazole.
was dried over anhydrous sodium sulfate and the
butanol was remoyed'by distillation. The re
maining material was distilled at reduced pres
25 sure, B. P. 200/226“ C./12 mm.,=and redistilled,‘
B. P. FIG-178° C./21/g mm.._ Yield of l-ethyl-Z-n
undecyl-4,5-dihydroimidazole, 23.5 grams.
This 5
material was dehydrogenated according to the
method of Example I. The product was l-ethyl
2-n-undecylimidazole.
'
This compound may be prepared by reacting a 80
The present invention is a continuation-in
mixture of 318 grams of the methyl ester of 2-n
part of copending application S. N. 498,584,
dodecenoic acid and 270 grams of anhydrous
?led August 13, 1943, which discloses the 4,5-di
ethylene diamine according to the method of
hydroimidazole derivatives from which the thera
Example I. They resulting N-(n-dodecen-Z-oyl-l)
peutic agents of the present invention may be
ethylene diamine may then be treated with an 35
derived.
'
hydrous calcium oxide according to the method
We claim:
of Example I to form ‘Z-(n-undecen-l-yl-l) -4,5
1. A compound of the group consisting of sub
dihydroimidazole. This product may then be re
stituted imidazoles of the formula type:
acted with dimethyl sulfate according to the 40
method of, Example I to form 1-methy1-2(n
undecene l-yl- 1) -4,5-dihydroimidazole. This ma
terial may then be dehydrogenated according to
the method of Example I. The product is sub
stantially 1 - methyl- 2 -(n-undecen-1-yl-1) -imi
dazole.
-
EXAMPLE IHV
-' 1 -alZyl-2-(n-tridecen-1 -'JZ-1) -imidazole
CH—N——R
(‘5H 6-K.
N
in which R represents an acyclic hydrocarbon
radical having from 1 to 5 carbon atoms in its
structure and R1 represents an acyclic hydro
carbon radical having from 10 to 16 carbon atoms
in its structure and acid salts thereof, prepared
for use astherapeutic agents.“
60
>
.
2. Substituted imidazoles of the formula type:
(|JH—N—R
dH o-m
This compound may be prepared by reacting
N
1.5 moles of the methyl ester of Z-n-tetradecenbic
acid with 4.5 molesiofzanhydrous ethylene di
amine according to the method of Example I.
in which R represents an acyclic hydrocarbon
radical having from 1 to 5 carbon atoms in its
structure and R1 represents a straight chain alkyl
radical having from 10 to 16 carbon atoms in
its- structure, prepared for use as therapeutic
The resulting N-(n-tetradecen-2-oyl-1) ethylene
diamine may then be treated with anhydrous
calcium oxide according to the method of Ex
ample I to form 2-(n-tridecen-1-yl-1)-4,5-di
hydroimidazole. This compound may then be re
acted with allyl chloride asin Example VII ac
cording to the method of Example II to form 1
agents.
_
'
3. The 1-methyl-2-n-undecyl-imidazole of the
formula:
'
CH—-N——CH3
allyl-2- (n-tridecen- l-yl- 1) -4,5-dihydroimidazole; 65
and if dimethyl sulfate is-used as the alkylating
agent the corresponding l-methyl compound is
formed. The material 1-allyl-2-(n-tridecen-l
yl-l) -4,5-dihydroimidazole may then be dehydro
genated according to the method of Example’ I.
The product is substantially l-allyl-z-(n-tride
cen-1-yl-1)-imidazole. ,
The
dehydrogenation
product of 1-methyl-2-(n-tridecen-l-yl-l)-4,5
dihydroimidazole is . substantially »1-methyl-2-,(n-'
tridecen-l-yl-l) -imidazole.v
1
prepared for use as a therapeutic agent.
4. The 1-methyl-2- (n-tridecene-l-yl-l) limi
dazole of the formula:
?H-NAJH;
c-oH=oH-(oHz)w-om
_oH
75 prepared for use as av therapeutic agent. >
-
'
2,404,300
10
5. The 1-methyl-2-n-tridecyl-imidazole oi the
formula:
‘ dehydrogenation catalyst and distilling o? the
dehydrogenation product.
_
7. A process for preparing compounds of the
<“3H--N-oH1
C--CH2-(CHz)u-CH:
formula type:
CH
\
CH—N—R
N
II
CH
prepared for use as a therapeutic agent.
6. A process for preparing compounds of the
formula type:
OH-——N—-’-R
(I511 é-QR:
N
a
10
|
%
C-Rr
in which R represents an acyclic ‘hydrocarbon
radical having from 1 to 5 carbon atoms-in its
structure and R1 represents a straight chain radi
cal having from 10 to 16 carbon atoms in its
structure, said process comprising reacting eth-"
in which R represents an acyclic hydrocarbon
ylene diamine with an‘ .alkyl ester of a mono
radical having from 1 to 5 carbon atoms in its 15 carboxylic group attached to a radical selected 7
structure and R1 represents an acyclic hydrocar
from the group of radicals de?ned hereinbefore‘ '
bon radical having from 10 to 16 carbon atoms
as R1, heating the acyl ethylene diamine deriva
in its structure, said process comprising reacting
ethylene diamine with an alkyl ester of a mono
carboxylic group attached to a radical selected
from the group of radicals de?ned hereinbefore
as R1, heating the acyl ethylene diamine deriva-;
tive thus formed in the presence of a mild dehy
drating agent, reacting, the derivative thus formed
tive thus formed in the presence of a mild de
hydrating agent, reacting the derivative thus
formed with an alkylating agent having at least
one hydrocarbon radical, each. of which is se
lected from the group of radicals de?ned herein
before as R, heating the derivative thus formed‘
with a dehydrogenation catalyst and distilling off
with an alkylating agent having at least one 25 the dehydrogenation product.
hydrocarbon radical, each of which is selected
from the group of radicals de?ned hereinbefore
LUcAs P. KYRlDES.
as R, heating ‘the derivative thus formed with a
FERDINAND B. ZIENTY.
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