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Патент USA US3064030

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United? States Patent O?fice
Patented Nov. 13, 1962
atom ring. The compound has the formula CqHa. It can
be represented by the following formula;
Geolfrey Wilkinson, London, England, assignor to Ethyl
Corporation, New York, N.Y., a corporation of Dela
No Drawing. Filed Aug. 8, 1958, Ser. No. 753,889
Claims priority, application Great Britain May 16, 1958
13 Claims. (Cl. 260-429)
This invention relates to novel organometallic com 10
pounds and a process for their preparation. More par
The cycloheptatriene compound which is a reactant in
ticularly, this invention relates to certain organic group
the process of this invention can be selected from a wide
VIB transition metal carbonyl compounds. An object of
range of cycloheptatriene organic compounds. The ap
this invention is to provide a novel class of organometallic
compounds. A further object is to provide a process for
the preparation of certain novel organic group VIB tran
plicable compounds include, for example, cycloheptatri
ene,‘ l-cycloheptatrienyl cycloheptatriene, l-methylcyclo
heptatriene, 2-isopropylcycloheptatriene, 1,4-diethy1cyclo
heptatriene, 4-phenylcycloheptatriene, 3-decylcyclohepta
triene, l-tert-butylcycloheptatriene, 1,3-diisopropylcyclo
heptatriene, 1-hydroxycycloheptatriene, l-cycloheptatri
sition metal carbonyl compounds. Other objects will be
apparent from the following description.
This invention comprises cycloheptatriene group VYIB
transition metal carbonyl coordination compounds. These
compounds may be represented by the formula:
enyl carboxylic acid propylester, 3-cycloheptatrienyl butyl
ether, Z-N-ethylcycloheptatrienyl amine, l-methylamino
cycloheptatriene, l-chlorocycloheptatriene, 3,5-di-methe
where A is a cycloheptatriene compound coordinated to
the metal, M, which itself represents a transition metal 25
of group VIB of the periodic table, namely chromium,
molybdenum and tungsten. The periodic table referred
to is that appearing in “Handbook of Chemistry and
Physics” 37th edition, pages 392 and 393 (Chemical
Rubber Publishing Company, 1955).
The compounds of this invention are prepared by a
process which comprises reacting a group VIB transition
metal carbonyl with an organic cycloheptatriene com
oxycycloheptatriene, l-di-methoxymethylcycloheptatriene,
3-isopropyl-1-phenylcycloheptatriene, l-methyl-4-pheny1
cycloheptatriene, 3-hydroxymethylcycloheptatriene, l-cy
cloheptatriene carboxylic acid, and the like. Those com
pounds having up to about 14 carbon atoms are preferred
since they lead to more easily recoverable products and
constitute the most readily available .cycloheptatriene
Whereas the process of the present invention can be
conducted at atmospheric pressure at the re?ux ‘tempera
ture of the system, higher or lower temperatures and
pound. It has been found that this preparation may be
higher pressures may also be conveniently employed. The
accomplished in a system where the only reactants are 35 most practical low temperature limit is the boiling tem
group VIB transition metal‘ carbonyls and the organic
perature of the particular cycloheptatriene compound
compound. When desired, the reaction can be conducted _ employed. In certain instances, it is desirable to conduct
in a high boiling solvent.
the reaction in the vapor phase by passing the vapor of
The process of this invention can be summarized by the
the cycloheptatriene compound over the metal carbonyl
following chemical equation in which A represents a
in a hot tube. When the reaction is conducted at super
cycloheptatriene compound and M represents a group
atmospheric pressure, temperatures of from 150° C._ to
VIB transition metal as de?ned above:
250° C. are preferred although temperatures outside this
range may also be employed. Since carbon monoxide is
Thus, carbon monoxide is given off as a product of this 45 given off as the product of this reaction, and an excess of
carbon monoxide, pressure may inhibit further forma
tion of the desired aromatic group VIB transition metal
The group VIB transition metal carbonyl compounds
tricarbonyl compound, it is advantageous to vent excess
which are reactants in the process of this invention in
monoxide through a condenser when the process
clude chromium hexacarbonyl, molybdenum hexacar
bonyl and tungsten hexacarbonyl. A preferred embodi 50 of this invention is conducted at elevated pressures.
A particularly preferred embodiment of this invention
ment of this invention comprises the reaction of molyb
reacting under re?ux conditions at atmospheric
denum hexacarbonyl with a cycloheptatriene compound
pressure, a cycloheptatriene compound, as de?ned above,
to produce a cycloheptatriene molybdenum tricarbonyl.
with group VIB transition metal carbonyl.
This embodiment is preferred as the compounds prepared
No solvent is required in conducting the process of
are highly useful chemical entities.
' 55
this invention, the cycloheptatriene compound being em
The temperatures employed in the process of this in
ployed in excess to serve as a carrier for the group VIB
vention may vary over a wide range. In general, tem
transition metal carbonyl. However, it is often con
peratures of from about 115° C. to 300° C. are employed.
to employ an inert diluent having a boiling point
However, a preferred range of temperature is from 115°
above about 115° C. in the process. High-boiling satu
C. to 225 ° C. as the reaction in this temperature range 60
rated hydrocarbons are the preferred solventsa Other
leads to a high yield of products with a minimum of un
desirable side reactions. Reaction times of from 1 to
solvents which can be employed include higher boiling
ethers, high-boiling aliphatic esters, silicone oils, aliphatic
10 hours or longer may be employed. Ordinarily, heating
periods of from 2 to 7 hours are su?icient to produce a
good yield of product.
Cycloheptatriene is a conjugated cyclic hydrocarbon
having 3 carbon-to-carbon double bonds in a 7 carbon
polyesters, and other liquids inert to the primary reactants.
Examples of the compounds useable as solvents in the
process of this invention include n-octane, n-nonane,
n-decane and the various iso-decanes and other para?nic
hydrocarbons having up toabout 20 carbon atoms, such.
3,064,022 1
Example V
A total of 100 parts of molybdenum hexacarbonyl and
as eicosane, octadecane, pentad'ecane and the like. Ether
solvents which may be employed include ethyloctylether,
amyl ethyl ether, ethyl heptylether, and ethyl hexylether,
200 parts of l-methylcycloheptatriene are heated at the
Ester solvents which may be employed’ include pentyl
boiling point of the methylcycloheptatriene for 1 hour in
400 parts of a high boiling methylphenyl polysiloxane.
Z-methylpropanoate, pentyl butanoate, butyl butanoate,
'y-methylbutyl butanoate, ethyl decanoate, methyl deca
Methylcycloheptatriene molybdenum tricarbonyl results
noate, pentyl hexanoate, ethyl hexanoate, and the like.
Applicable silicone oils include copolymers and homo<
from this reaction.
polysiloxanes, diphenyl polysiloxanes, di(chlorophenyl)
polysiloxanes, hexaethyldisiloxane, hexapropyl disilane,
tion produces a good yield of l-bromocycloheptatriene
Example VI
polymers of the various organo'siloxanes and organo
silanes having the appropriate boiling range. Examples 10 A total of 60 parts of tungsten hexacarbonyl and 130
parts of bromocycloheptatriene in 200 parts of decane
of these are the dimethyl polysiloxanes, methylphenyl
as a solvent, are heated at re?ux for 2 hours.
The reac
tungsten tricarbonyl.
diethyldipropyldiphenyldisilane and the like. The poly
Example VII
By heating 200 parts of 1, 3-di-ethoxycycloheptatriene
esters applicable as solvents in the process of this inven
tion are completely esteri?ed dicarboxylic acids. Esters
may be employed derived from succinic, maleic, pyrotar
and 40 parts of chromium carbonyl at re?ux for 10 hours,
taric, glutaric, ,adipic, pirnelic, suberic, azelaic, sebacic
and pinic acids; speci?c esters being di(1-methyl-4-ethy-l
di-ethoxycycloheptatriene chromium tricarbonyl is pro
Example VIII
o'ctyl) glutarate, di(Z = ethylhexyl) adipate, 'di(3'- methyl
butyllaxelate, di(Z-ethylhexylhzelate, di(Z-ethylhexyD
Following the procedure of Example I, molybdenum
‘sebacate, iii-(3,5,5 '- trimethylhexyhsebacate, di(2 - ethyl
carbonyl and 'l-methyl-4-pheny1cycloheptatriene are re
hexyDmaleat'e, di(methylcyclohexyl)adipate, Z-ethyl
hexyl-l-methylheptylsebacate, and the like.
The vcy‘clohep'tatriene group VIB transition metal car
bonyl compounds prepared by the process of this inven
acted to produce methylphenylcycloheptatriene molyb
denum tricarbonyl.
Example IX
The apparatus consists of a vessel equipped with heat
tion‘can be recovered by evaporation of the excess cyclo~
h'eptatri'ene reactant and solvent. The compounds may
ing means and a conduit for passing vapor into a ther
mal reactor tube which is also equipped with heating
be puri?ed by recrystallization from hydrocarbons or
30 means so that a vaporized liquid may be passed over
lower aliphatic ethers.
The following examples, in which all parts and per
the solid reactant in the thermal reactor tube.
of this invention and their preparation.
Example I
he'p‘t'at'riene and molybdenum hexacarbonyl is placed in
the reactor tube. The system is then ?ushed with nitro
gen and a continuous ?ow of nitrogen is maintained above
To ‘a reaction vessel ?tted with a re?ux condenser,
the cycloheptatriene and passes with the cycloheptatriene
was charged 156 parts of molybdenum carbonyl and
vapor over the molybdenum carbonyl in the reactor tube.
The reactor tube is heated and maintained at about 140”
about 80 parts of cycloheptatriene. The mixture was
heated at reflux ‘temperature, about l16—118° C. for 7
C. The cyclohep'tatriene is heated to the boiling point
and the cycloheptatriene vapor is carried over the molyb
denum carbonyl in the reactor tube. Cycloheptatriene
molybdenum tricarbonyl is isolated in the cold trap.
Example X
Following the procedure of Example VI, the cyclo
heptatrieneone is reacted with molybdenum hexacarbonyl
After ‘the heating period, the excess unreacted
cyclohep'tatriene was removed under vacuum.
ing the reactor tube is a cold trap for isolating reaction
products. The vessel is charged with a quantity of cyclo
c'en'ta'g'es are by weight, are illustrative of the compounds
The re
sulting deep red solid ‘was then extracted with several por
tions of low boiling petroleum ether (about 40-60° C.).
The combined extracts were ?ltered and the resulting solu
ti'oii'wa's ‘cooled to —'7 8° "C. on an acetone Dry-Ice bath.
The'co'olin'g ‘caused precipitation of deep red crystals
which‘were removed by 'filtr'a'tion ‘and recrystallized ‘again
from ‘petroleum ether. ‘The resulting cycloheptatriene
molybdenum ‘carbonyl ‘was ‘further puri?ed by sublima
in ethyl hexyl ether as a solvent to yield cyclohepta
trieneone molybdenum tricarbonyl.
tion in a high vacuum a't'75—'8‘5'° C. on to an ice-cooled 50
probe. ‘The yield of'pure cycloheptatriene molybdenum
Following the procedure ofExarnple I, l-hydroxy
carbonyl, having a melting point of 99.6“ ‘C. was 69 parts.
methylcycloh'eptatriene 'is reacted ‘with tungsten hexacar
Example 11
The procedure. of vExample I was followed employing
chromium hexacarbonyl instead of molybdenum hexa
Example XI
’ Example XII
In a pressure resistant vessel equipped with heating
means, a temperature measuring device and means for
carbonyl. Cycloheptatriene chromium tricarbonyl was
charging and discharging gaseous, liquid and solid react
is placed 160 parts of molybdenum hexacarbonyl
pound has no definite melting point ‘but decomposes above 60
and 1000 parts of cycloheptatriene. The vessel is then
about 90° C.
sealed ‘and the temperature raised to 225° C. This tem
Example III
peratureis maintained for 6 hours with ‘the charge over
produced at approximately 40 percent yield. This com
Proceeding according to themethod of outlined in Ex
ample ‘I, molybdenum Ihexacarbonyl was heated at re?ux
with .phenyl cycloheptat-riene-and an excess of petroleum
ether (Bl). .120". C.). Thereaction produced phenyl
cycloheptatriene molybdenum tricarbonyl.
Example IV
Cycloh‘epta'trienyl cycloheptatriene and molybdenum
carbonyl in ‘an “excess of petroleum ether (BP. 120° C.)
' were heated together to the, re?ux temperature of the
system to produce a good yield of cyclobeptatrienyl cyclo
he‘ptatriene molybdenum tricarbonyl.
100 pad. of nitrogen pressure. The vessel is then cooled,
vented and discharged and'the reaction worked up as de
scribed in Example I. An excellent yield of cyclohep
tatriene molybdenum tricarbonyl results.
Example XIII
‘Following the procedure of Example XII, 100 parts of
70 tungsten hexacarbonyl and SQOparts of phenylcyclohep
tatriene are reacted in‘ 600 parts of di( l-methyl-4-ethyloctyl)glutarate at 300° for 1 hour.
triene tungsten tricarbonyl results.
The compounds of the present invention vary insofar
75 as ‘their thermal stability is “concerned, but all of them
can be decomposed at a temperature above 400° C. The
thermal decomposition of the compound results in the
to about 14 carbon atoms and M is a transition metal of
group VIB of the periodic table.
formation of metallic mirrors comprising a layer or coat
ing of a particular group VIB transition metal. These
2. The compound of claim 1 wherein M is molybde
metallic layers and coatings have useful and desirable 5
properties of electrical conductance, furnish protection
against corrosion when they are applied to base materials
3. Cycloheptatriene molybdenum tricarbonyl.
4. Cycloheptatriene chromium tricarbonyl.
5. A cycloheptatriene metal carbonyl coordination
compound having the formula:
susceptible to corrosion and likewise have a decorative
effect. The compounds of the present invention can also
be deposited on glass, glass cloth, resins and other in 10
sulating supports, and the resultant metal-coated material
where A is an organic cycloheptatriene compound con
can be used as conductors and insulating tapes for elec
sisting of atoms selected from the class consisting of
trical applications. The metals can be deposited on the
carbon, hydrogen, oxygen, nitrogen and halide atoms and
support in the desired proportions by thermal decom
containing from 7 to about 14 carbon atoms in which
position using classical processes in order to obtain the 15 the cycloheptatriene ring is substituted only with radicals
so-called “printed” electrical circuits. Similarly the metals
selected from the group consisting of hydrogen, alkyl,
can be applied to metallic supports to increase the corro
sion resistance and on glass or asbestos cloth to obtain
decorative metallic surfaces and designs. In order to
hydroxy, amino, alkoxy, halogen, aryl, carboxyalkyl,
hydroxyalkyl and carboxy and M is a transition metal
of group VIB of the periodic Table.
6. A process for preparing a cycloheptatriene group
VIB transition metal carbonyl compound which com
prises reacting a group VIB transition metal hexacarbonyl
effect the deposition of the metals by thermal decomposi
tion of the compounds of the present invention, it is pre
ferred to use inert gases, e.g., argon, as protecting or
covering gas in order to reduce to a minimum oxidation
by air or oxygen.
with an organic cycloheptatriene compound consisting of
atoms selected from the class consisting of carbon, hy
drogen, oxygen, nitrogen and halide atoms and contain
Deposition on glass cloth illustrates the applied
processes. A glass cloth band weighing 1 gram is dried
for one hour in an oven at 150° C.
ing from 7 to about 14 carbon atoms in which the cyclo
heptatriene molecule is substituted only with radicals
Then together with
0.5 gram of cycloheptatriene chromium tricarbonyl it is
selected from the group consisting of hydrogen, alkyl,
enclosed in a glass tube devoid of air and heated at 400°
hydroxy, amino, alkoxy, halogen, aryl, carboxyalkyl, hy
C. for one hour, after which time the tube is cooled and 30 droxyalkyl and carboxy.
opened. The cloth has a uniform metallic gray appear~
7. Process of claim 6 where the group VIB transition
ance and exhibits a gain in weight of about 0.02 gram.
metal carbonyl is molybdenum carbonyl.
The cloth has a greatly decreased resistivity. Each in
8. The compounds of claim 1 wherein A is cyclo
dividual ?bre proves to be a conductor. As would be
expected, the application of a current to the cloth causes
9. The compounds of claim 8 wherein M is molybde
an increase in temperature. Thus, a conducting cloth
has been prepared. This cloth can be used to reduce
10. A process for preparing cycloheptatriene group
static electricity, for decoration, for thermal insulation
VIB transition metal carbonyl compounds in which the
by reflection, as protection and as a heating element.
cycloheptatriene group is a hydrocarbon group contain
The chemical entities of the present invention can be 40 ing from 7 to about 14 carbon atoms, which method com
used to deposit the respective group VTB transition ele
prises reacting a group VIB transition metal hexacar
ments in the catalytic form on suitable supports. Thus,
bonyl compound with a cycloheptatriene hydrocarbon
the compounds of the present invention can be thermally
compound containing from 7 to about 14 carbon atoms.
decomposed using elevated temperatures of 250400” C.
11. The process of claim 10 wherein said group VIB
or above, preferably in an atmosphere of argon or other 45 transition metal hexacarbonyl is molybdenum hexacar
inert gas, e.g., krypton, in order to obtain supported group
VIB transition elements in the catalytically active form.
12. Process of claim 11 wherein the reaction is con
Other classical processes can be used to deposit the metal~
ducted at the re?ux temperature of the system.
lic catalysts, using the chemical entities according to the
13. The process of claim 7 wherein the reaction is
present invention. For example, a solution of methyl 50 conducted at the re?ux temperature of the system.
cycloheptatriene molybdenum tricarbonyl is mixed with
infusorial earth, the compound being adsorbed on the
infusorial earth. The adsorption product is separated
by ?ltration and heated in air to decomposition tempera
ture of the methyl cycloheptatriene tricarbonyl, yielding
a catalytically active surface of molybdenum oxide. The
catalyst is useful in the re?ning of petroleum fractions.
The catalyst can also be deposited on alumina.
I claim:
References Cited in the ?le of this patent
Veltman ______________ __ Oct. 8, 1946
Wilkinson: “J. Am. Chem. Soc.,” vol. 76, No. 1,
January 5, 1954, p. 209.
Piper et al.: “J. Inorg. Nuvl. Chem.,” vol. 3, 1956, p.
1. A cycloheptatriene metal carbonyl coordination 60 104.
Abel et al.: Proceedings of the Chem. 800., pp. 152-153
cycloheptatriene organic compound consisting of atoms
(May 1958).
selected from the class consisting of carbon, hydrogen,
Hallam et al.: Journal of the Chem. Soc. (London),
oxygen, nitrogen and halide atoms and having from 7
65 pp. 642-645 (February 1958).
compound having the formula AM(CO)3 where A is a
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