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Патент USA US3033895

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United States Patent 0 “Ce
Patented May 8, 1962
one or more of the hydrocarbon radicals attached to the
group IV-A metal of the above described- reactant is re
Richard D. Gorsich, Baton Rouge, La, assignor to Ethyl
Corporation, New York, N.Y., a corporation of Dela
placed by a [halogen having an atomic number from 17
to 5 3, inclusive, i.e., chlorine, bromine or iodine. Of the
carbonyl ligand reactants, triphenyltin manganese tetra
carbonyl triphenylphosphine is particularly preferred be
No Drawing. Filed Apr. 28, 1961, Ser. No. 106,166
4 Claims. (Cl. 260-42937)
cause of its ease of preparation, because of its relative
volatility and solubility in organic solvents which mark
edly facilitate its puri?cation and reaction in the instant
This invention relates to a novel process for the manu
facture of certain useful bimetallic compounds, speci?
process, and because of the ease of synthesis of the com
cally, halo and organo halo metallic manganese carbonyl 10 ponent compounds from which it is prepared. Of the
ligand compounds wherein the metals of the halo and
halogen reactants, chlorine is particularly preferred be
organo halo metallic groups are members of group
cause of its economy and accessibility. Thus, a partic
IV-A of the periodic system of the elements.
ular embodiment of this invention is the reaction of chlo
Heretofore, certain organic and inorganic metal car
rine with triphenyltin manganese tetracarbonyl triphenyl
bonyls have been suggested as gasoline additives, pri
phosphine. Other embodiments will be evident as the
marily for the purpose of increasing the antiknock rat
discussion proceeds.
ings of the gasolines. For example, manganese penta
Illustrative of the carbonyl ligand reactants are triphen
carbonyl is a highly effective antiknock agent both when
ylsilicon manganese tetracarbonyl trimethylphosphine, tri
used as the sole antiknock agent and when used in com
bination with alkyllead antiknock compounds, e.g., tet»
r'aethyllead. Effective as many of these carbonyl com
pounds may be, however, they all exhibit certain short
comings in use which materially decrease their value for
the stated purpose. For example, their use is generally 25
associated with more or less severe engine wear and with
a shortened useful life of the exhaust valves.
It is a
speci?c and valuable property of the compounds pro
duced by the process of this invention that they mini
mize these particular problems; as a result of their un
usual chemical structure they do have good antiknock
properties and yet they do not have the above substan
tial adverse effects of markedly increasing engine wear
and impairing exhaust valve durability.
Accordingly, it is an object of this invention to pro
vide a novel and effective method for the preparation of
useful halo and organo halo metallic manganese carbonyl
ligand compounds wherein the metals of the halo or or
gano halo metallic group are members of group IV-A
of the periodic system of the elements. Another object
is to provide a novel and effective method for the prep
aration of such compounds in high yield and purity. A
further object is to provide a more e?icient method for
producing compounds which exhibit the good antiknock
effectiveness of manganese carbonyls but which are free
from the marked disadvantages of shortened exhaust
valve life and high engine wear associated with the use
of prior metallic carbonyls in general. These and other
important objects of this invention will become apparent
The novel process of this invention is an organic rad
ical replacement process wherein a triorgano group IV-A
manganese tetracarbonyl ligand compound is reacted with
a halogen.
The organo group IV-A metal manganese
tetracarbonyl ligand reactant is represented by the gen
eral formula
methylgermanium manganese tetracarbonyl triallylarsine,
triethyltin manganese tetracarbonyl tri-u-naphthylstibine,
trioctyllead manganese tetracarbonyl tricetylphosphite,
tricetylsilicon manganese tetracarbonyl trimesitylarsine,
trivinylgermanium manganese tetracarbonyl triethylan
timonite, triallyltin manganese tetracarbonyl tribenzyl
phosphite, tribenzylllead manganese tetracarbonyl tri
phenylarsenite, tricyclopentadienylsilicon manganese tet
racarbonyl trivinylstibine trimesityl-germanium manga
nese tetracarbonyl tri-m-cumenylphosphine, tri-o-cumen
yltin manganese tetracarbonyl trioctylarsine and tri-a
naphthyllead manganese tetracarbonyl tricyclopentadien
ylantirnonite. Of these carbonyl ligand reactants, the
.triaryltin manganese tetracarbonyl ligand compounds, es
pecially triphenyltin manganese tetracarbonyl triphenyl
phosphine, are preferred because of their ease of separa
tion and because of their solubility in organic solvents
which markedly facilitates their puri?cation and reaction.
The process of this invention is carried out by bringing
the reactants together in the presence or absence of a
4.0 solvent and generally, but not necessarily, at a moderately
elevated temperature. Preferably, the reactants are com
bined at a temperature in the range of -—B0 to 150° C.
Temperatures in the range of -—l0 to 100° C. are pre
ferred because under these conditions the reaction pro
ceeds at a satisfactory rate, the reactants and products
exhibit adequate stability, and these temperatures are with
in the liquid range of the preferred selected solvents if
such are used. When lead compounds are employed,
reaction temperatures in the rangeof ~30 to 0° C. are
particularly preferred, since some cleavage at the metal
metal bond of the carbonyl ligand reactant sometimes
occurs at higher temperatures. The solvents employed
may be either low-boiling or high-boiling depending upon
the reaction temperatures and pressures desired. Thus, if
the reactions are to be carried out at or near ambient
temperature and at atmospheric pressure, low-boiling sol
vents are satisfactory, whereas if it is desired to carry
In this formula, MIV represents an element of group IV-A
of the periodic system of the elements having an atomic
out the reaction at elevated temperatures, high-boiling
15 to 51, inclusive, i.e., phosphorus, arsenic or antimony;
ethyl amyl ether, ethyl isoamyl ether, ?-chloroethyl ether, ~
?-bromoethyl ether and bis~chloromethyl ether. Among
solvents may be used'at atmospheric pressure or low
number from 14 to 82, inclusive, i.e., silicon, germanium, 60 boiling solvents and elevated pressure may be used.
Typical of the lower boiling solvents which can be used
tin or lead; E is an element of group V-A of the periodic
system of the elements having an atomic number from
are the following: toluene, ethyl benzene, chlorobenzene,
R is a hydrocarbon radical preferably having up to about
18 carbon atoms and R’ is a hydrocarbon or oxyhydro
carbon radical preferably having up to about 18 carbon
atoms. The hydrocarbon radicals and the hydrocarbon
portions of the oxyhydrocarbon radicals may be alike or
di?erent. The hydrocarbon radicals are preferably alkyl,
‘the high-boiling solvents which may be employed are a
chloron-aphthalene, 18-chlorohaphthalene, 1,2 - dichloro
naphthalene, benzyl butyl ether, benzyl ethyl ether, butyl
phenyl other, butyl-o~tolyl ether, butyl-m-tolyl ether, butyl
p-tolyl ether, heptyl phenyl ether and bis(p-chlorophenyl)
alkenyl, aryl, cycloalkyl, aralkyl or alkaryl radicals, and 70 ether.
‘the oxyhydrocarbon radicals are preferably alkyl, aryl,
It is preferred to use the reactants in essentially stoichio~
cycloalkyl, aralkyl or alkaryl radicals. In this process
metric proportions of one equivalent of halogen per
7 8,033,886
equivalent of hydrocarbon to be displaced from the group
IV—Aw metal of the carbonyl ligand compound, because
problems of separation and recovery are thereby reduced,
is added. The mixture is stirred for a half hour at 22—29°
C. The product obtained is tribromotin manganese tetra
carbonyl triethylstibine.
but- a slight excess of one reactant or the other may be
Example 1V
used,,if desired, the reaction toward completion.
Moreover, if complete replacement of the hydrocarbon
3.04 parts of tricetyllead manganese tetr-acarbonyl tri
ethylphosphite, dissolved in 137 parts of ethylene dichlo
groups attached ‘to the group IV-A metal is desired, a
ride, is placed in a ?ask and cooled to ~25 to —-30° C.
substantial excess of halogen may be used without the
by means of a freezing mixture. Dry nitrogen is bubbled
occurrence of signi?cant amounts of undesirable side re
10 through liquid bromine at room temperature and the
bromine-laden nitrogen is introduced into the solution in
The reaction proceeds smoothly and rapidly under the
prescribed conditions, reaching completion for the halo
genation .of the loweralkyl and aryl derivatives in 10
the ?ask. _ Passage of the bromine is continued for one
hour. The ?ask is allowed to warm to room temperature
and tribromolead manganese tetracarbonyl triethylphos~
minutes to. 1/2 hour,‘ particularly when a solvent is used.
Somewhat longer reaction times are desirable for the 15 ph-ite is obtained.
what shorter reaction times are satisfactory for the lowest
Example V
Tricyclopentadienylsilicon manganese tetracarbonyl tri
octylphosphine (1.90 parts) and chlorine (0.35 part) are
alkyl derivatives, particularlyif the reactions are carried
dissolved in 86 parts of hexane. The solution is stirred
more highly substituted aryl derivatives and for those
derivatives containing'highly substituted ligands. Some
out in the absence of solvents and of diluents for the 20 for 10 minutes at 22-28“ C. 'Cyclopentadienyl dichloro
silicon manganese tetracarbonyl trioctylphosphine is obhalogen reactants. In any-event, reaction periods up to
about 3 hours are quite- adequate for good yields.
tained ingood yield.
Example VI
The carbonyl ligand ‘reactants can readily be prepared
bythe reaction of an alkali‘ metal manganese tetracarbonyl
tetracarbonyl trioctylarse
ligand complex Wi-than organometallic halide of a metal 25 ni-te (2.54parts) and chlorine (0.35 part) are dissolved
of‘ group IV-A of the periodic system, i.e., silicon,
in 114 parts of benzene. The mixture is stirred for l'hour
germanium, tin or lead, or by the reaction of an organo
at 32-43° C. Mesityldichlorosilicon manganese tetracar
group?IVéA metal manganese pentacarbonyl with the ap
bonyl trioctylarsenite is obtained.
propriate ligand. Both reactions proceed, rapidly when
Example VII
the components are stirred together in tetrahydrofuran 30
solution at room temperature.
When 3.06 parts of triphenylsilicon manganese tetra-.
The products of thernovel process of this invention are
carbonyl tricetylstibine ‘and a solution'of 0.80 part of
' of‘consider'able value in the chemical and allied arts.
bromine in petroleum naphtha are mixed and the mixture
For-example, they are potent antiknock agents and in this
is heated for 2yhoulrs under re?ux with 138 parts of pe
utility. they are versatile agents in that they are highly 35 troleum vnaphtha, phenyldibromosilicon manganese tetra
e?e'ctive in both unleaded and conventional leaded gaso
carbonyltricetylstibine is obtained.
lines made from 1a Wide variety of base stocks. An ad
Example VIII
ditional feature of these compounds is that when they are
used ‘as antiknock agents the engine wear andexhaust
VA mixture of, trimethylgermauium manganese tetra
valve durability‘ characteristics of the engine are not 40 carbonyl tricetylphosphite (2.60 parts), bromine (0.80
markedlyimpaired, which is the situation brought about
part) and tetralin (117 parts) is heated to 45~52° C. for
a period of 2 hours. The product is methyldibromo
byzthe use of metallic carbonyls heretofore known and so
employed. A further advantage of these compounds is
that, owing to the presence of halogen in the compounds,
germanium .manganese tetracarbonyl' tricetylphosphite.
Example IX
the amount of halogen scavenger required to be used in
the fuel along with the conventional antiknock compounds
When a mixture of 1.21 parts of triethylgermanium
manganese tetracarbonyl trivinylarsine, 1.27 parts of io
dine and 54 parts of benzyl ethyl ether is heated at 74—86‘‘
is greatly‘reduced.
The invention will be more fully understood by ref
erence to the following illustrative examples in which all
parts and‘percentages are by weight.
C. for a period of 2 hours, ethyldiiodogermanium manga
nese :tetracar-bonyl trivinylarsine is obtained in good yield.
, Example X
Example I .
A mixture of 2.06 parts of trioctylgermanium manga
nese tetracarbonyl triallylstibine, 1.27 parts of iodine and
93 parts of butyl phenyl ether is heated at 90~102° C.
for 2 hours.- .The product is octyldiiodogermanium man
Gaseous ‘chlorine was passed through a solution of 2.0
parts (0.0026 mole) of triphenyltin manganese tetracar
bonyl triphenylphosphine in 90 parts of methylene chlo—
ride at a moderate rate for 10 minutes. vEvaporation of
the solvent left a solid that recrystallized from a mixture
ganese tetracarbonyl triallylstibine.
Example XI
of methylene chloride and n-h'exane to give 1.1 parts (65
percent yield) of white needles which analyzed for tri
chlorotin manganese tetracarbonyl triphenylphosphine.
Analysis.—Calculated for Cl3SnMn(CO)'4P(C5H5)3: C,
40.38; H, 2.31. Found: C, 40.25; H, 2.46;
Example 11
Chlorine mixed-with 2 volumes ofair as a diluent is
bubbled for '1 hour'at'a temperatureof0-10o C. through
3.17 parts of tricetyltin manganese tetracarbonyl triben
zylphosphine is dissolved in 143 parts of ethyl amyl ether
and 0.18‘ part of chlorine is introduced into the solution.
The resulting mixture is heated f0r;1 hour at 43-52“ C.
Dicetylchlorotin manganese tetracarbonyl tribenzylphos
phine is thus obtained in‘ good yield.
Example XII
2.39partsjof-tribenzyltin manganese tetracarbonyl tri
earbonyl triphenylarsenite in7 77 parts'of chloroform. The
benzylarsenite: is treated with 107 parts of ethyl-p-hromo
.isolvent' is evaporated leaving a residue which uponre
ethyl'ether.v and‘ 0.18V‘part of‘rchlorine. 'Reaction for l
. icryst-allizationfrom' benzene yields trirchlorotinv manganese
70'20-'-27° C; resultsrin the formation of dibenzyL
tetracarbonyl triphenylarsenite.
‘ .
' a‘ solution of‘1.71 ‘parts ofitrirnethyltin manganese tetra
Example III
chlorotin manganese tetracarbonyltribenzylarsenite.
Example , XIII
To 1.45 parts of triethyltin manganese tetracarbonyl tri
' To 2.40 parts of tricyclopentadienyltin manganese tetra
ethylstibine, dissolved in>65 parts of carbontetrachloride,
108 parts. of di-p-chloro
‘a solutionpof 20 parts of bromine in carbon tetrachloride
ethyl ether and 0.40 part of bromine are added and the
mixture is heated at 113—1l8° C. for 21/2 hours. The
product is dicyclopentadienylbromotin manganese tetra
invention thereby. Employing the procedures illustrated
Example XIV
therein and the process of this invention, other products
are produced by appropriate substitution of the carbonyl
The above examples have been presented by way of
illustration and it is not intended to limit the scope of the
carbonyl tri-m-cumenylstibine.
ligand reactants described hereinbefore. Thus, employing
When 2.92 parts of trimesityllead manganese tetracar
the process of this invention, the following products are
also produced in high yield from stoichiometric propor
bonyl tri-m-cumenylphosphite and 0.40 part of bromine
are mixed with 131 parts of bis-chloromethyl ether, previ
ously cooled to —25 ° C., and maintained at this tempera
ture for a period of 3 hours, dimesitylbromolead manga
tions of the appropriate reactants: trichlorosilicon man
dibromopropylgermanium manganese tetracarbonyl tri
decylarsenite, iododibutyltin manganese tetracarbonyl tri
vinylphosphine, tribromolead manganese tetracarbonyl tri
isooctylantimonite, diiodoethylsilicon manganese tetracar
nese tetracarbonyl tri-m-cumenylphosphite is obtained in
good yield.
Example XV
To 1.66 parts of phenyldimethyltin manganese tetracar
ganese tetracarbonyl tris(methylcyclopentadienyl)stibine,
bonyl tridodecylarsine, chloro-bis-(Z-indenyl)germanium
bonyl tricyclopentadienylarsine, 0.18 part of chlorine dis
manganese tetracarbonyl tribenzylphosphite, triiodotin
solved in 88 parts of bis-p-chlorophenyl ether is added.
The mixture is heated to l43~154° C. and is maintained
at that temperature for 1 hour. The product is dimethyl
lead manganese tetracarbonyl tri-a-naphthylarsenite, and
chlorotin manganese tetracarbonyl tricyclopentadienylar
manganese tetracarbonyl tripropylstibine, dichloromesityl
bromodimethylsilicon manganese tetracarbonyl tris(2
Other examples of the products
20 ?uorenyl)-phosphine.
obtainable in high yield by the process of this invention
will be evident.
In carrying out the process of this invention, the reac
Example XVI
Trimethyltin manganese tetracarbonyl tricyclopenta
dienylantimonite (1.72 parts), ethyl-B-bromoethyl ether
tants are normally combined as indicated above in ap
tions employed can vary from a 100 percent or greater
excess by weight of the halogen reactant (when a trihalo
(88 parts) and iodine (0.64 part) are heated together for
3-hours at 65—75‘’ C. Dimethyliodolead manganese tetra
carbonyl tricyclopentadienylantimonite is obtained.
Example XVII
derivative is desired) to a 100 percent or greater excess
of the carbonyl ligand reactant (when a monohalo deriva
30 tive is desired). The amount of the excess is obviously
limited to some extent by the particular product desired.
A mixture of triethylsilicon manganese tetracarbonyl
A slight excess of one reactant or the other, as about 10
trimesitylphosphine (1.68 parts), benzene (76 parts) and
chlorine (5 parts) is reacted for 20 minutes at 22—3l° C.
The product is trichlorosilicon manganese tetracarbonyl
proximately stoichiometric proportions but the propor
percent by weight, is often used to bring about an in
creased reaction rate. In any event, when an excess of
35 one reactant is used the product consists of a mixture of
Example -X VIII
To 3.38 parts of tricetylsilicon manganese tetracarbonyl
trimesitylarsenite, 152 parts of carbon tetrachloride are
added and chlorine is bubbled into the resulting solution 40
for a half hour at 21-330 C. The product is trichloro
compounds which can be separated by taking advantage
of differences in solubility or other physical or chemical
properties. However, the product compounds need not
be separated, but can be employed as obtained in the re
action mixture.
As indicated above, the reactions of this invention are
usually carried out by bringing the components together
silicon manganese tetracarbonyl trimesitylarsenite.
Example XIX
in solution.
The solvents are compounds or mixtures
which are essentially inert and preferably liquid under
the reaction conditions. Thus, they may include essen
1.95 parts of trivinylsilicon manganese tetracarbonyl
tri-u-naphthylstibine is added ‘to 88 parts of ethylene
dichloride and bromine diluted with 2 volumes of methane
is bubbled through the solution in the absence of light.
tially inert hydrocarbons such as hexane, octane, cetane,
benzene and the like; halohydrocarbons such as ethyl
chloride, methylene dichloride, the chloro?uoromethanes,
a-tri?uorotoluene, chlorobenzene, m-dichlorobenzene and
Reaction for 11/2 hours at 44-55 ‘’ C. results in the for
mation of tribromotin manganese tetracarbonyl tI‘l-rx 50 the like; ethers such as diethyl ether, di-n-butyl ether,
?-chloroethyl ethyl ether, bis-?-chloroethyl ether, benzyl
ethyl ether, benzyl ‘butyl ether, butyl phenyl ether, butyl
o~tolyl ether, butyl-m-tolyl ether, butyl-p-tolyl ether,
Example XX
heptyl phenyl ether and bis(p-chlorophenyl)ether and
tetracarbonyl tri-a-naphthylphosphite is mixed With 109 55 the like; and mixtures of any of the foregoing. Chloro
parts of chlorobenzene and nitrogen saturated with bro
alkanes are especially preferred as solvents, particularly
When 2.43 parts of tribenzylgermanium manganese
mine is bubbled into the solution for 1 hour at 19-28” C.,
those containing up to six carbon atoms. The solvent
tribromogermanium manganese tetracarbonyl tri-a-naph
of choice is methylene chloride because of its low boiling
point and its relatively high solubility for the reactants
thylphosphite is obtained.
Example XXI
2.14 parts of tricyclopentadienylgermanium manganese
tetracarbonyl triS-Z-indenylarsine and 13 parts of iodine
(these being of particular value in that they facilitate
separation of the solvent and recovery of the product)
and because of its accessibility and ease of preparation.
Under some conditions, the halogen reactants are em
are mixed and the mixture is dissolved in 96 parts of m
dichlorobenzene. The solution is stirred for 3 hours at
ployed in the gaseous phase, and thus can simply be
65 bubbled through the reaction mixture. However, when
23~30° C. The product is triiodoger-manium manganese
used in the gaseous phase, they may be mixed with in
tetracarbonyl tris-Z-indenylarsine.
ert diluents for the purpose of reducing the activity of the
halogen and preventing over-halogenation. Any diluent
Example XXII
inert to the reactants and products may be used. The
A mixture of 3.04 parts of trimesitylgermanium man
compounds are stable on exposure at reaction tempera
ganese tetracarbonyl tris-2-?uorenylstibine and 137 parts
ture to dry nitrogen which can thus be used with safety.
of hexane is heated to 37~46° C. and 9 parts of iodine
are added. The mixture is maintained at the above tem
Other suitable diluents include dry air, carbon dioxide,
low-molecular-weight gaseous hydrocarbons and the noble
perature for 3 hours. The product is triiodogermanium
gases helium, neon, argon, hryston and xenon.
manganese tetracarbonyl tris-Z-?uorenylstibine.
Because the reactions ordinarily proceed at satisfac
10_mil1imeters of mercury to 100 ‘atmospheres may be
used if desired, provided a liquid reaction system is main
tained at least in part.
for ‘the bimetallic ligand compounds, it is not intended
tobe limited-except as set forth in thefollowing claims:
tory rates under normal pressure conditions, atmospheric
pressure is usually satisfactory but pressuresranging from
I claim:
1. The method of preparing-lacompound represented
_ by the general formula
The normally solidproducts of the process are soluble
in and can be puri?ed by recrystallation from a variety‘
which comprises reacting a halogen having an atomic
of organic solvents. Speci?cally, simple aromatic sol
number from 17 to 53, inclusive, with a compound repre
vents such as benzene or toluene, simple aliphatic sol
vents such as hexane, alcohols such as ethanol,‘ and halo 10 sented by the general formula
hydrocarbons such as methylene chloride and carbon
tetrachloride and their mixtures are satisfactory.
As stated above, the products obtained ‘according to
wherein X is a halogen having an atomic number from
this- invention are useful as antiknock agents for internal
17 to 5 3, inclusive; MIv is an element selected from group
IV-A of the periodic system of the elements and having
combustion engine fuels. They may suitably be employed
in concentrations varyingfrom that corresponding to
an atomic number from 14 to 82, inclusive; E is an ele
about 0.005 gram of manganese per gallon to their satura
tion concentrations at ambient temperature. They 'are
ment selected from group V-A of the periodic system of
the elements and having an atomic number from 15 to 51,
inclusive; R is a hydrocarbon radical having up to about
highly e?ective agents and their versatility is shown by the
fact that theycan be added to the fuel either alone or in 20 18 carbon atoms; R’ is a radical selected from the group
combination with other antiknock agents such’ as'tetra
ethyl-lead. For example, the addition of‘0.01 gram of
manganese per gallon astrichlorolead manganese tetra
consisting of hydrocarbon andoxyhydrocarbon radicals.
having up to about 18 carbon atoms; and n is an integer
from 0 to 2, inclusive.
car-bonyl triph'enylphosphine to a‘ catalytically' cracked
2. The method of claim 1 wherein said halogen is
gasoline increases the octane number thereof; Similar r 2.5. chlorine.
such enhancement in the octane number of fpuelsis ob
3. The method of claim 2 wherein the reaction is car
tained vemploying other products of vthis invention._
ried out in a chloroalkane asa-solvent.
Furthermore, the bimetallic compoundsproduced by
4. The method for producing trichlorotin manganese
the process are subject to thermal decomposition at ele
tetracarbonyl triphenyl phosphine which comprises're.
vated temperatures, as about 150° C. and higher, so that v3.0 acting a solution of triphenyltin managanese tetracar
bonyl triphenylphosphine ‘in liquid methylene chloride
theycan beused toplate an alloy of the component:
metals on a suitable substrate by contacting the heated
substrate with the appropriate compound. The tin com
poundsof thisinvention are also excellent thermal stabil
izers for polyvinyl chloride and the like, and are effec
tive; fungicides and slimicides.
Other uses for the products of this invention, willnow.
be evident.
Having. thus described the novel process of ‘synthesis
with an excess of elementary’ chlorine. 7
References Cited in the ?le of this patent
Kaufman _____ -2. ____ __ Nov. 3, 1959
Kaufman ___________ __ Jan. 26, 1960
Kaufman -7 ____ _V______ Jan. 26, 1960
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