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Патент USA US3026354

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United States Patent O??ce
Patented Mar. 20, 1962
heat soaking the monomer at elevated temperatures, e.g.
50° to 210° C. for a period of several hours may be
William J. Craven, Elizabeth, and Herbert K. Wiese,
Cranford, N.J., assignors to Esso Research and En
gineering Company, a corporation of Delaware
No Drawing. Filed Oct. 29, 1958, Ser. No. 770,303
9 Claims. (Cl. 260-439)
This invention relates to a novel process for the prep
As the cobalt containing reactant, there may be em
ployed any cobalt compound such as oil soluble fatty
acid ‘salts of cobalt, inorganic salts, metallic cobalt pref
erably where the surface has been activated or, if desired,
preformed cobalt carbonyl.
Thus, for example, there
can be employed the salts of cobalt and higher molecular
weight fatty acids such as stearic, oleic, naphthenic, lin
aration of cyclopentadienyl cobalt carbonyl including hy
drocarbon-substituted cyclopentadienyl cobalt carbonyl
compounds. More speci?cally, this invention relates to
the preparation of the aforesaid cyclopentadienyl cobalt
carbonyl compounds by a single step process.
oleic and the like. Water soluble salts of organic acids
may include cobalt acetate, cobalt formate and the like.
As inorganic salts, there may be employed cobalt chlo
are also useful as oil-soluble oxo catalysts.
the term “cobalt carbonyl” it is intended to include such
ride, cobalt bromide, cobalt iodide, cobalt sul?de and
Oyclopentadienyl and substituted cyclopentadienyl co 15 oxides such as cobaltous and cobaltic oxides. When
employing a cobalt halide or sul?de, it may be desirable
balt carbonyls of this invention are known to have anti
to use a halogen acceptor such as metallic copper. By
knock qualities and are useful as gasoline additives. They
For simpli
?cation, the term “a cyclopentadiene compound” will be
employed to include a hydrocarbon-substituted cyclo
pentadiene and dimers thereof. The term “cyclopenta
diene cobalt carbony” is also intended to include the
hydrocarbon-substituted cyclopentadiene cobalt carbonyl
compounds, i.e. CpCo(CO)2, where Cp is any cyclo
compounds as Co2(CO)8, H[Co(CO)4] and [Co(CO)3].,.
To obtain an active metallic cobalt having a surface sub
stantially free of oxides, sul?des and the like, cobalt salts
such as cobalt oxalate may be decomposed to form cobalt
oxide at temperatures of 125° to 250° C. and the cobalt
oxide reduced with hydrogen at elevated temperatures of,
for example, 300° C. to obtain the active metallic cobalt.
25 Another technique for obtaining metallic cobalt having
In accordance with the prior art, the preparation of
an active surface is to treat a cobalt-aluminum alloy with
cyclopentadienyl cobalt carbonyl involved several steps.
aqueous sodium hydroxide to dissolve away the alumi
It was ?rst necessary to produce the sodium cyclopenta
num leaving highly active metallic cobalt. It is evident,
dienyl compound which was then reacted with a neutral
cobalt salt to form the cyclopentadienyl cobalt salt, which 30 therefore, that cobalt in almost any form may be em
ployed for the reaction of this invention since under re
in turn was reacted with carbon monoxide to yield the
action conditions, if cobalt carbonyl is not employed, it
desired cyclopentadienyl cobalt carbonyl. While this
will be formed in situ from any cobalt containing com
process is satisfactory for the production of these cobalt
carbonyl compounds, the required three stages have ob
As the carbon monoxide containing gas, it is preferred
vious economic drawbacks with regard to commercial 35
to employ essentially pure carbon monoxide; however,
impure gases may be utilized as long as the impurities do
It has now been discovered that cyclopentadiene, hydro
not interfere with the principal reactant. For example,
carbon-substituted cyclopentadiene, or their dimers may
a hydrogen'containing carbon monoxide gas may be em
be reacted with cobalt comprising material at elevated
temperatures under carbon monoxide pressures to effect 4:0 ployed if a hydrogen de?cient component is utilized in
the reaction mixture to absorb the hydrogen and thereby
the direct production of the desired cyclopentadienyl co
avoid substantial hydrogenation of the cyclopentadiene
balt carbonyl compounds.
reactant. A hydrocarbon reactant is preferably employed
The following general formula represents the class of
to absorb any hydrogen formed in the reaction. This
cyclopentadiene compounds suitable as reactants for the
hydrocarbon may be the cyclopentadiene compound itself
present process:
pentadiene compound.
or some ole?n, such as hexene, pentene, octene, cyclo
hexene and others. Although the use of a large excess
or dimers thereof
of a cyclopentadiene compound to absorb any hydrogen
formed in the reaction is not detrimental to the reaction,
it is generally undesirable from a standpoint of vproduct
work-up. Generally the cyclopentadiene cobalt carbonyl
wherein each of the R’s represent the same or di?erent
products boil close to the dimers or hydrogenated dimers
radicals selected from the group consisting of hydrogen
and hydrocarbon radicals. As examples of various com
pounds coming within the scope of the above formula,
?cation ‘of the products di?icult. While the stoichiomet
ric reaction requires one mole of the cyclopentadiene
there are Z-methyl cyclopentadiene, 2-ethyl cyclopenta
diene, 2-isopropyl cyclopentadiene, 1,4-dimethyl cyclopen
tadiene, l-methyl-4-ethyl cyclopentadiene, l,2,3,4-tetra
methyl cyclopentadiene, 2-tertiary butyl cyclopentadiene,
2-isopropenyl cyclopentadiene, 1-hexyl-2-(2-phenyl pro
pyl) cyclopentadiene, 2-phenyl cyclopentadiene, 3,4-di
cyclopropyl cyclopentadiene, 2-tolyl cyclopentadiene,
phenyl-butyl cyclopentadiene, l-methyl cyclopentadiene
of the cyclopentadiene compounds, thus making the puri
dimer or two moles of the cyclopentadiene monomer for
two moles of cobalt compound, it is preferred to employ
a ratio of cobalt to cyclopentadiene monomer ranging
from 1/3 to 3/1. If desired, a hydrocarbon solvent may
be employed in a volume ratio of 1/10 to 10/1. The
60 solvent may comprise any ole?n, particularly an ole?n
capable of reacting with any hydrogen formed in the re
action, benzene, toluene, xylene, heptane and others.
Temperatures for the reaction vary between 100-3000
and l-butyl cyclopentadiene and similar hydrocarbon
substituted cyclopentadienes. The particular hydrocar 65 C. and even this range may be exceeded on either end
to obtain the desired results. Carbon monoxide pressure
bon substituent is not of critical importance with regard
may be maintained between 500 and 10,000 p.s.i.g. ‘In
to the operability of the present process since the hydro
general, the higher carbon monoxide pressures permit a
carbon substituents do not interfere with the principal
faster reaction rate with higher conversions and yields
reaction; however, preferred reactants are the C0—C8
for a given period of time. Good contact between the
alkyl cyclopentadienes and/ or their dimers.
To obtain the dimer of the cyclopentadiene compound 70 carbon monoxide gas and liquid reactants in accordance
with known techniques is desirable for optimum results,
from the monomer, any well-known technique such as
although the process is operable by merely pressuring a
Example 4
reactor, containing the cobalt and cyclopentadiene re
actant, with carbon monoxide gas.
The cyclopentadiene cobalt carbonyls are distillable
under reduced pressure from the reaction mixture and
may be stored for appreciable periods of time in an inert
atmosphere. If some unconverted cyclopentadiene dimer
distills over With the cyclopentadienyl cobalt carbonyl,
A pressure reactor was charged with 38.5 grams (0.58
mole) of dicyclopentadiene, 221 grams of cobalt oleate
(0.43 mole) and 650 ml. xylene. The mixture was heated
to 180—190° C. for 8 hours with 3000 p.s.i.g. carbon
monoxide. The mixture was then distilled and 60 grams
of a dark red liquid boiling between 58° to 80° C. at 20
mm. was collected. The product contained 54 grams of
other means such as extractive distillation, solvent extrac
tion or fractional crystallization can be employed.
If 10
desired, the solution of cyclopentadienyl cobalt carbonyl
several microns to about 250 mm. To simplify the dis
tillation and thus obtain a high purity product, it is gen
erally important to select the ratio of cobalt/cyclopenta
What is claimed is:
1. A process for the preparation of a cyclopentadienyl
cobalt carbonyl which comprises reacting a stoichiometric
in hydrocarbons may be used as such as a fuel additive.
The preferred technique of separation, however, in
volves distillation under reducedpressure ranging from
cyclopentadienyl cobalt carbonyl (65% yield).
excess of a cyclopentadiene dimer compound selected
from the group consisting of dimers of cyclopentadiene
15 and C0—C8 alkyl cyclopentadienes, and dimers thereof
with a cobalt containing reactant selected from the group
consisting of oil soluble cobalt salts of fatty acids and
diene compound in the reactor in such a manner as to
metallic cobalt under a carbon monoxide pressure of
minimize the amount of unconverted cyclopentadiene
from 500 to 10,000 p.s.i.g. and at a temperature from
20 100° to 300° C. and wherein said excess is employed
For a clearer understanding of the present invention,
as a hydrogen acceptor to absorb hydrogen liberated
reference may be had to the following examples which
during the reaction.
set forth various processes for the production of cyclo
2. A process in accordance with claim 1 wherein said
pentadienyl cobalt carbonyl compounds.
compound is di-cyclopentadiene.
3. A process in accordance with claim 1 wherein said
Example 1
compound is di-methylcyclopentadiene.
cobalt carbonyl which comprises reacting a stoichiometric
mole) of Raney cobalt metal, 120 grams (0.7 mole) of
methylcyclopentadiene dimer and 200 ml. of benzene sol
4. A process for preparing methyl cyclopentadienyl
A pressure reactor was charged with 24 grams (0.4
The mixture was then heated to 210° C. with a
gauge reading of 1700 p.s.i.g. carbon monoxide pressure
and a temperature was maintained in the closed reactor
for a period of about 12 hours. The crude reaction
mixture obtained was ?ltered free of unreacted metal
powder and distilled. The fraction boiling at 55-65° C.
at 5 mm. pressure was collected and found to contain
methylcyclopentadienyl cobalt carbonyl
excess of di-methylcyclopentadiene with metallic cobalt
under a carbon monoxide pressure of from 500 to 10,000
p.s.i.g. and at a temperature of from 100° to 300° C.
5. A process in accordance with claim 1 wherein the
cobalt-containing reactant is cobalt oleate.
6. A process in accordance with claim 1 wherein an
ole?n is employed as the hydrogen acceptor.
7. A process in accordance with claim 1 wherein said
compound is the dimer of 2~isobutyl cyclopentadiene.
8. A process for preparing cyclopentadienyl cobalt car
which comprises reacting a stoichiometric excess
(MCPD Co(CO)-2)
of dicyclopentadiene with cobalt oleate under a carbon
monoxide pressure of from 500 to 10,000 p.s.i.g. and at
as well as nnreacted methylcyclopentadiene dimer. In- '
a temperature of from 100° to 300° C.
frared analysis of the distillate showed the characteristic
9. A process for preparing isobutyl cyclopentadienyl
metal~carbonyl absorption peaks at 1960 cm.—1 and 2030
cmfl. The fraction weighed 33 grams and contained 45 cobalt carbonyl which comprises reacting a stoichiometric
excess of 2-isobutyl cyclopentadiene dimer with metallic
3.62% cobalt.
Example 2
The conditions of Example 1 are repeated employing
5000 p.s.i.g. to obtain larger yields of methylcyclopenta 50
dienyl cobalt carbonyl.
Example 3
A reactor was charged with one mole of Raney cobalt
and 1.5 moles of 2-isobutyl cyclopentadiene dimer with 55
350 mm. heptane solvent. The mixture was heated to
250° C. with a carbon monoxide pressure or" 650 p.s.i.g.
for a period of 3 hours to obtain substantial yields of iso
butyl cyclopentadienyl cobalt carbonyl.
cobalt under a carbon monoxide pressure of from 500 to
10,000 p.s.i.g. and at a temperature of from 100° to
300° C.
References Cited in the ?le of this patent
Anzilotti et al. _______ __ May 7, 1959
Piper et a1.: J. Inorganic and Nuclear Chemistry, vol. 7
I, pp. 165-174 (1955).
Sidgwiclr: Chemical Elements and Their compounds,
p. 1422 (1950).
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