вход по аккаунту


Патент USA US3053632

код для вставки
United States Patent O?ice
Patented Sept. 11, 1962
carbon carbanion and not the "alkali metal cation. This
is in accord with the theory described by De Paul, Lipkin
Harold E. Podail and Hyrnin Shapiro, Baton Rouge, La.,
and Weisman in an article in volume 78, J.A.C.S., page
116 (1956) to the effect that in these alkali metal com
plexes the metal exists as a cation ‘and the ring system
exists as an anion. Examples of the polycyclic aromatic
assignors to Ethyl Corporation, New York, N.Y., a cor
poration of Delaware
No Drawing. Filed July 29, 1.960, Ser. No. 46,087
9 Claims. (Cl. 23-203)
alkali metal complex are sodium .biphenyl complex, po
tassium biphenyl complex, lithium biphenyl complex,
sodium anthracene complex, rubidium anthracene com
This invention relates to the manufacture of metal 10 plex, lithium anthracene complex, sodium phenanthrene
complex, sodium naphthalene complex, lithium naph
carbonyls of the group Vl-B metals of the periodic table.
thalene complex, cesium naphthalene complex, and the
Where the term “periodic table” is used herein, reference
like. From a cost-effectiveness standpoint, the complexes
is made to The Periodic Chart of the Elements, copy
of sodium are the most efficient and hence are preferred.
right 1957 and revised 1958 by The Fisher Scienti?c Com
These polycyclic aromatic alkali metal complexes are pre
pany, Chicago, Illinois.
pared by reacting the alkali metal directly With'the aro
The group VI-B metal carbonyls, chromium, molyb<
matic hydrocarbon in the presence of a diluent. There
,_._~ldenum and tungsten hexacarbonyl, have been known for
have been numerous examples and methods described in
a long period of time. There have been several methods
the literature for the preparation of these aromatic hy
published in the literature for the production of these
drocarbon alkali metal addition compounds, some of
metal carbonyls. One particular method was described
which are US. Patents 2,019,832, 2,023,793, 2,125,401,
(Brimm et al., US. Patent 2,803,525) where an iodide
salt of ‘a group VI~B metal was reacted in an oxygenated
aliphatic medium with a reducing metal higher than
2,146,447 and 2,150,039.
An especially important feature of this invention is
the fact that the process takes place at a low temperature.
platinum in the electromotive series, i.e., magnesium,
sodium, and the ilke, and carbonylation effected by the 25 While the process can be run over a broad range of tem
use of a carbon monoxide atmosphere. According to
the patentees it was necessary to use, or form in situ, the
iodide salt in ‘order to effect the reaction.
Iodine and
iodides are expensive and therefore this process is not as
economical as would be desirable. Other methods of
preparation of the group VI-B metal carbonyls involved
peratures from about ——20° C. to 100° C., the more espe
cially preferred temperatures range from below about 0°
C. to about 30° C. A very signi?cant feature, then, is
that this reaction can take place at room temperature
with great efficiency. Consequently, there is no need to
encumber the reaction equipment with elaborate and cost
ly heating or refrigerating means.
the use of a Grignard reagent as a reducing agent in the
The inert diluents which can ‘be used in the process of
presence of carbon monoxide to form the metal carbonyl.
this invention are those in which the polycyclic aromatic
These processes have also proven undesirable from the
35 alkali metal complex is soluble. Examples of these inert
standpoint of economy.
solvents are hydrocarbons, amines, and, preferably,
It is an object of this invention to provide an economi
cal method for the preparation of metal carbonyls of
group VI-B in the periodic table, i.e., chromium, molyb
ethers. Polyethers are particularly preferred, especially
the diethylene glycol dialkyl ethers.
phere of carbon monoxide at superat-mospheric pressure
that the product can be hydrolyzed in the presence ofair.
It is important that this reaction take place in an atmos
denum and tungsten. 5It is a further object of this inven
tion to provide an effective process which is simple in 40 phere of carbon monoxide at superatmospheric pressure.
The precise pressures at which there is a carbon monoxide
operation and one in which the reactants are inexpensive
uptake are dependent upon the particular reactants and
and plentiful. It is also an object of this invention to
reaction temperatures used. In general, however, the
provide a process free from the shortcomings experienced
pressure can be from about 300 p.s.i. to about 10,000
in processes invented heretofore. Other objects of this
p.s.i. The more particularly referred pressure, however,
invention will be patently obvious from the following de
is from about 800 p.s.i. to about 3500 p.s.i.
scriptions and claims.
The reaction product can be hydrolyzed under a va
The above and other objects of this invention are
riety of atmospheres such as air or carbon monoxide in a'
achieved by reacting a group VI-B metal halogen salt—
dilute aqueous mineral acid at a temperature from about
preferably a chloride—with a- polycyclic aromatic alkali
0° C. to 30° C. One feature of this process is the fact
metal complex in an anhydrous inert diluent in an atmos
su?icient to result in an up-take of carbon monoxide and
and at room temperature.
One of the most unique features of this process is the.v
then hydrolyzing the reaction product. The halide salts
agent which is a polycyclic aromatic alkali metal
of the group Vl-B metals are ?uorine, chlorine, bromine 55
complex. As indicated above, it is commonly accepted
and iodine. The most common and preferred halide salts
that the ‘alkali metal in the complex exists in an oxidized
are chromium trichloride, molybdenum pentachloride and
(i.e., in the +1 valence state) whereas the polycyclic
tungsten hexachloride. However, other group VI-B
aromatic hydrocarbon exists in the negative state as a
metal halide salts, such as CrCl2, CrBrz, M012, MoFz,
carbanion (i.e., in the-1 valence state). Hence, in the
like can M‘QCL},
be used.M0016,
salts are
WC15, and
in the 60 process of this invention it de?nitely appears that the.
negative polycyclic aromatic hydrocarbon radical reduces
anhydrous form since water adversely affects the reaction
the group VI—B metal halogen salt thus freeing the group
forming the metal carbonyls.
VI—B metal to react with carbon monoxide, thereby form
The polycyclic aromatic alkali metal complex is pro
the metal hexacarbonyl. In this process the negative,
duced from any of the polycyclic aromatic hydrocarbons 65 polycyclic
aromatic hydrocarbon radical is oxidized to a
capable ‘of forming the so-called addition compounds , free polycyclic aromatic hydrocarbon.
with an alkali metal.
Examples of the polycyclic aro
This is very
' vividly demonstrated by the fact that the polycyclic aro
matic hydrocarbons are biphenyl, anthracene, phenan
matic hydrocarbon can be recycled and used again in~the
threne and naphthalene. Without desiring to be bound
process. Therefore, the experimental evidence leads to
by any theoretical considerations, it de?nitely appears 70 the conclusion that the polycyclic aromatic hydrocarbon
that the actual reducing agent in the polycyclic aromatic
carbanion is the actual reducing agent and that the alkali
alkali metal complex is the polycyclic aromatic hydro
metal plays no direct role in the reduction.
The product is hydrolyzed with 30 parts by volume 6
Among the numerous advantages of this process is the
normal phosphoric acid at 25° C. in the presence of car
fact that the reagents may be contacted above 0° C. with
bon monoxide. The product recovered is molybdenum
out excessive over-reduction of the group VI-B metal
halogen to the metal state. Such over-reduction is char
acteristic of certain prior processes and is disadvan
Example VIII
tageous in that the metal so reduced is in such form as
To 3.2 parts chromium trichloride is added 120 parts
it does not react to form the carbonyl. Another ad
of triethylene glycol dimethyl ether under- 1,000 p.s.i. of
vantage of this invention is the fact that the reducing
carbon monoxide. 1:1 sodium naphthalene complex (8
agent may be pumped in solution to the reactor contain
ing the group VI-B metal halide and the carbon monox 10 parts) is pumped into the reactants over a period of 3
hours at 65° C. For recovery of the product, the re
ide. This is an especially good feature since metallic
actants are cooled to 25° C. and 50 parts by volume of 6
molten sodium is di?icult to pump under pressure. Sodi
molar aqueous hydrochloric acid is pumped in under 800
um in the molten state tends to agglomerate and thus
p.s.i. of carbon monoxide over a period of 2 hours. To
hinder the reaction.
The process of this invention will be more fully under 15 this is added 100 parts by volume of Water and the
chromium hexacarbonyl is separated and recovered by
stood by reference to the following examples in which all
steam distillation.
parts are by Weight unless otherwise specified.
It will be noticed that in the preceding examples the
Example I
term 1:1 was used in conjunction with the alkali metal
Anhydrous chromium trichloride (3.2 parts) in 120 20 polycyclic aromatic hydrocarbon complex. This means
that the ratio of the alkali metal is one gram atom to one.
parts by volume of diethylene glycol dimethyl ether, as
mole of the polycyclic aromatic hydrocarbon.
an inert solvent, was reacted with 18 parts of 1:1 sodium
The temperature at which the reaction is conducted is
naphthalene complex under a pressure of 3500 p.s.i. of
critical in order to obtain high yields of the desired
carbon monoxide at 25 ° C. for 18 hours. To the re
action mixture was added 50 parts ‘by volume of 6 molar 25 metal carbonyl. Thus, the reaction should be carried out
from about —20° C. to about 100° C. A more preferred
hydrochloric acid under 800 p.s.i. of carbon monoxide
over a period of 2 hours at 0° C. The product recovered
was chromium hexacarbonyl.
temperature range is from below about -—0° C. to about
30° C. At temperatures above 70° C. the yield of the
desired metal carbonyl is appreciably diminished.
Example II
The time of the reaction depends on other conditions
Anhydrous chromium trichloride (3.2 parts) in 120
under which the reaction is conducted, especially tem
parts by volume of diethylene glycol dimethyl ether was
perature and solvents, although times between a few
reacted with 18 parts of 1:1 sodium naphthalene complex
minutes and several hours are generally quite adequate.
It is usually preferred to conduct the reaction for a period
100° C. for 6 hours. This product was hydrolyzed with 35 of from about 45 minutes to about 18 hours.
50 parts by volume of 3 molar hydrochloric acid at 25 °
The proportions of the reactants can also be varied and
C. in air. The product recovered was chromium hex
are generally based upon the amount and particular
metal salt of the group VI-B metal halides present. The
mole ratio between the alkali metal polycyclic aromatic
Example III
40 complex and the group VI-B metal halide salt ranges
Chromium trichloride (1.6 parts) is reacted with 5.3
from about 2:1 to about 8:1. The optimum mole ratio
parts of 1:1 sodium biphenyl complex in 30 parts of di
between the alkali metal polycyclic hydrocarbon com
ethylene glycol butyl ether under a pressure of 1500 p.s.i.
plex and chromium halides ranges between about 2:1 to
of carbon monoxide at 20° C. for 6 hours. The product
about 6: 1. In the case of chromium trihalides, the more
is hydrolyzed and recovered as in Example I. The prod
preferred mole ratio is from. 3:1 to 5:1. The optimum
uct is chromium hexacarbonyl.
mole ratio between alkali metal hydrocarbon complexes
and molybdenum salts ranges from about 3:1 to about
Example 1V
under a pressure of 3500 p.s.i. of carbon monoxide at
7:1 'while the more preferred mole ratio is from 5:1 to
7:1. The optimum mole ratio between the alkali metal
14 parts of 1:1 sodium anthracene complex in 30 parts
complex and the tungsten halide salts is from about 2:1
tetrahydropyran in the same manner as Example I. The 50 to about 8:1: while the more preferred range is from
product which is obtained is molybdenum hexacarbonyl.
about 6:1 to about 8:1. It should be noted that where an
inordinate amount of the alkali metal hydrocarbon com
Example V
plex is used an excessive reduction of the metal halide to
Tungsten hexachloride (4 parts) is reacted with 16
free metal could result thus impairing the reaction.
parts of 1:1 sodium phenanthrene complex in 35 parts
The reducing agents which can be employed in this
anisole under a pressure of 1000 p.s.i. of carbon monox
invention are polycyclic aromatic hydrocarbons which
ide at 25° C. for 10 hours. The product is hydrolyzed
will form the so-called addition compounds with the
with 25 parts by volume of 6 normal sulfuric acid at 25°
alkali metals. The polycyclic aromatic hydrocarbons
C. in the presence of carbon monoxide. The product
which may be reacted with the alkali metals to form the
Molybdenum pentachloride (2.7 parts) is reacted with
60 aromatic alkali metal complex are naphthalene, biphenyl,
recovered is tungsten hexacarbonyl.
phenanthrene, acenaphthene, anthracene, retene, as Well
Example VI
as homolog (e.g., alkyl derivatives) of these hydrocar
Chromium trichloride (3.2 parts) is reacted with 18
parts 1:1 sodium naphthalene complex in the presence
The inert diluents which may be used are any inert hy
of 120 parts tetrahydrofuran under a pressure of 800 65 drocarbon compounds. The more particularly preferred
p.s.i. of carbon monoxide at 20° C. for 14 hours. The
product is hydrolyzed with 50 parts by volume 6 molar
acetic acid at 25° C. in the presence of carbon monoxide.
The product recovered is chromium hexacarbonyl.
Example VII
Molybdenum pentachloride (2.7 parts) is reacted with
11 parts 1:1 sodium naphthalene complex in the presence
diluents, however, are those in which the alkali metal
complex is soluble. The polyethers are particularly de
sirable as diluents in this process. Typical examples of
70 suitable ethers are diethyl ether, diisopropyl ether, di
butyl ether, methylphenyl ether (anisole), phenyl ether,
p-tolyl ether, ethylene glycol dimethyl ether, diethylene
glycol methyl ethyl ether, diethylene glycol dibutyl ether,
triethylene glycol dimethyl ether and other alkyl ethers
of the 35 parts of isopropyl ether under a pressure of
1200 p.s.i. of carbon monoxide at 24° C. for 8 hours. 75 containing from 1 to 10 carbon atoms per alkyl ‘group.
Cyclic ethers such as tetrahydrofuran, tetrahydropyran
and dioxane can also be used. Other examples of dil
elusive, with an addition product between a polycyclic
aromatic hydrocarbon and an alkali metal, the hydro‘
carbon portion existing as a carbanion and the alkali
metal existing in the +1 valence state, the reaction being
uents are pyridine, triethylamine, mesitylene, toluene,
piperidine, and the like.
The hydrolytic agents capable of being used in the
conducted in an inert solvent and in an atmosphere of
carbon monoxide at a superatmospheric pressure su?i
cient to result in an uptake of carbon monoxide, the mole
hydrolytic carbonylation step of this process can be se
lected from a broad group of compounds. These hy
drolytic agents must be capable of donating a hydrogen
ratio between the said addition product and the metal
halogen salt ranging from about 2:1 to about 8:1; and
water, methyl alcohol, ethyl alcohol, hydrochloric acid, 10 then hydrolyzing the reaction mixture.
2. The process of claim 1 wherein the alkali metal of
sulfuric acid, phosphoric acid, acetic acid, and the like.
the polycyclic aromatic hydrocarbon addition product is
It will be noted that the acids used in this hydrolysis are
not oxidizing acids. In general, dilute aqueous mineral
3. The process of claim 1 wherein the inert solvent is
acids are useful for this purpose. The more preferred
an ether.
and cheaper hydrolytic agent is hydrochloric acid which
4. The process of claim 1 wherein the solvent is a di
can be used either in a gaseous state or in an aqueous
ethylene glycol dialkyl ether.
This process provides products which are of consider
5. The process of claim 1 wherein the halogen of the
metal halogen salt of the group VI~B metal is chlorine.
able use. These products can be subjected to high tem
peratures, thereby providing decomposition to obtain the 20 6. The process of claim 1 wherein the metal halogen
salt of the group VI-B metal is chromium trichloride.
respective metals in a ?nely divided form. For example,
7. The process of claim 1 wherein the metal halogen
when molybdenum carbonyl is heated at a temperature
salt of the group VI-B metal is molybdenum penta~
above 250° C. in an inert atmosphere, a ?nely divided
pyrophoric product is obtained which is useful in elec
8. The process of claim 1 wherein the metal halogen
tronic tubes for anodes and support members or in alloy 25
salt of the group VI-B metal is tungsten chloride.
ing in making steels. The carbonyls of the metals chro
9. A process for the manufacture of chromium hexa
mium, molybdenum and tungsten and mixtures thereof or
carbonyl which comprises reacting chromium trichloride
with other carbonyls, in various atmospheres, can be de
with a sodium-naphthalene addition product and carbon
composed on metal surfaces, such as steel to give resistant
coatings, which are stable at high temperatures. These 30 monoxide in a diethylene glycol alkyl ether solvent at a
temperature from about -—20° C. to about 30° C. and at
valuable metals can also be produced in extremely pure
A few examples of these hydrolytic agents are
a pressure from about 800 to about 3500 psi, the mole
ratio between the said addition product and the chro
mium trichloride ranging from about 2:1 to about 8:1;
as chemical intermediates in preparing organometallic
35 and then hydrolyzing the reaction mixture with dilute
aqueous mineral acid.
Having thus described the process of this invention it
is not intended that it be limited except as set forth in
References Cited in the ?le of this patent
the following claims.
We claim:
1. A process for the manufacture of carbonyls of the 40 2,880,066
Closson et al. ________ __ Mar. 31, 1959
metals of group VI—B of the periodic table of the ele
Closson et a1 _________ __ Mar. 31, 1959
ments having atomic numbers from 24 to 74, inclusive,
Podall ______________ __ Sept. 13, 1960
which comprises reacting a metal halogen salt of a group
Podall ______________ __ Sept. 13, 1960
VI-B metal having an atomic number from 24 to 74, in
Podall et al. _________ __ Sept. 13, 1960
form and are sui?ciently ductile for structural purposes
as in aircraft fabrication. These products are also useful
Без категории
Размер файла
483 Кб
Пожаловаться на содержимое документа