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Патент USA US3080309

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Patent lice
Fatented Mar. 5, teas
2
it
which is displaced from the metal does not polymerize
but instead is halogenated to a saturated cyclic hydro’
carbon.
3,680,305
MANUFACTURE 0F CYCLCE’ENTADIENYL
Typical examples of compounds which may be made in
METAL HALEDES
Richard D. Gorsich, Baton Rouge, La, assignor to Ethyl 5 accordance with the present‘ invention are cyclopent-a
Corporation, New York, N.Y., a corporation of‘ ‘Vir
dienyl titanuirn trichloride, cyclopentadienyl titanium tri
ginia
chloride, cyclopentadienyl titanium tribromide, and cor
No Drawing. Filed July 31, 1958, Ser. No. 752,294
responding metal halide compounds containing ethyl
5 Claims. (Cl. 204-158)
cyclopentadienyl-, butylcyclopentadienyl-, octylcyclo-pen
tadienyl-, dimethylcyclopentadienyl-, dihexylcyclopenta
dienyl-, vinylcyclopentadienyb, ethynylcyclopentadienyl-,
This invention relates generally to cyclopentadienyl
metal halides and more particularly a process for the
phenylcyclopentadienyl-, methylphenylcyclopentadienyl-,
manufacture of monocyclopentadienyl metal halides of
metals of groups lV-B, V-B ‘and molybdenum and con
taining three or four halogen groups, depending upon the
metal.
I
The compounds manufactured by the process of this in
vention have only recently been discovered and represent
acetylcyclopentadienyl-, allylcyclopentadienyl-, benzylcy
clopentadienyl-, tolylcyclopentadienyl- and other like rad~
15 icals.
. Other cyclopentadienyl metal halide compounds which
can be made by the process of this invention are cyclopen
tadienyl zirconium trichloride, methylcyclopentadienyl
some of the few known stable organo compounds of
these metals. The compounds are useful as catalyst
zirconium tribromide, cyclopentadienyl hafnium trichlo
components for polymerization of olei'ins, as intermediates 20
for the manufacture of other compounds and, due to
their hydrocarbon solubility, are useful as additives to
fuels such as gasoline, fuel oils, diesel fuels, and the like.
It is accordingly an object of this invention to provide
ride, phenyl cyclopentadienyl hafnium tri?uoride, cyclo~
pentadienyl vanadium trichlonide, methylcyclopentadienyl
vanadium tribroinide, cyclopentadienyl niobium tetra
a new and novel process for the manufacture of cyclo 25
pentadienyl halogen compounds of metals of groups 1V~
B, V433 and molybdenum. Another object is to provide
an improved process which will produce the above com
pounds economically and in high yield. Another object
chloride, methylcyclopentadienyl niobium tetrabromide,
cycloperttadienyl tantalum tetrachloride, methylcyclopen
tadienyl tantalum tetrachloride, octylcyclopentadienyl
tantalum tetrabromide, phenylcyclopentadienyl tantalum
tetrachloride, cyclopentadientyl molybdenum tetrachlo
ride, methylcyclopentadienyl molybdenum tetrachloride,
octylcyclopentadienyl molybdenum tetrabromide and the
is to provide a process which will provide halogenated 30 like.
Compounds containing mixed halogens can also be
cyclic hydrocarbons as a by-product. Other objects and
made
by the process of this invention. Thus, bis(cyclo
advantages of the present invention will be more ap
pentadienyl) metal halides of any of the above~1nentioned
parent in the following description and appended claims.
halides can be reacted with different elemental halogens
It has now been found that these and other objects of
form mixed monocyclopentadienyl metal halides con
the invention can be accomplished by reacting b-is(cyclo 35 to
taining
three or four halogen atoms. Generally, bis
pentadienyl) metal halides directly with the coresponding
(cyclopentadienyl) metal dihalides or trihalides can be
reacted with an elemental halogen to form monocyclopen
elemental halogens to form the desired monocyclopenta
dienyl metal halides, having one additional halogen atom
tadienyl metal compounds containing two different halo
gens. Typical examples of these compounds are cyclo
relative to the ‘starting material, and also halogenated
cycloaikanes corresponding to "the number of carbon
atoms in the cyclopentadienyl group. More particularly,
the process comprising reacting a bis(cyclopentad-ienyl)
metal halide having the general formula
pen'tadienyl titanium dichloride bromide, cyclopenta
dienyl titanium chloride dib-romide, cyclopentadienyl ti
tanium dichloride ?uoride, cyclopentadienyl titanium
bromide di?uoride, cyclopent-adienyl molybdenum triehlo
ride bromide and the like.
In general, the preferred compounds of this invention
have three halogens in all compounds containing titani
wherein Cp is a cyclopentadienyl group or a substituted
cyclopentadienyl group; M is a group IV-B, V-B or
um, zirconium, hafnium and vanadium, whereas the
compounds have four halogens in compounds containing
bromine and ?uorine; and n is from 2 to 3 inclusive.
The process is generally carried out at a temperature of 50 one of the metals niobium, tantalum and molybdenum.
In the preferred compounds of the present invention
from about —50° to about 300° C., preferably 20° to
the cy-clopentadienyl moiety contains from 5 to 15 car
150° C. The process can be conducted in the absence of
bon atoms and includes not only alkyl and aryl substi
a solvent but when no solvent is employed, it is preferred
molybdenum metal; X is a halogen, especially chlorine,
tuted cyclopentadienyl groups but also includes indenyl
including substituted indenyl
to ‘employ conditions wherein the halogen is in a liquid
state. However, solvents are frequently desirable at the 55 and lluorenyl derivatives,
and ?uorenyl derivatives.
more elevated temperature conditions. The process can
As pointed out above, the reaction of this invention
can be conducted at temperatures ranging from about
—50°- to about-300° C., and is preferably conducted at
The process of this invention for manufacture of vthe
cyclopentadienyl metal halides is particularly simple, 60 temperatures of about20° to 150° C. Lower tempera
tures‘can vbe employed except that the reaction rate is
economical and useful for commercial production of these
normally quite slow and the cost is increased due to
compounds. it is particularly surprising, however, that
be carried out in the absence or in the presence of a - '
catalyst.
bis(cyclopentadienyl) metal compounds of this type can
be halogenated directly with the elemental halogen since
refrigeration requirements. The upper temperature
limit is normally controlled by the degree of decomposi
it is known that halogens do ‘tend to effect complete cleav
age of the cyclopentadienyl groups from the metal, even
with such extremely stable compounds as ferrocene [bis
compounds of this invention can be conducted, if desired,
tion of the reactants or product, but with some of the
v(cyclopentadienyl) iron]. Of special signi?cance is the
at temperatures even above 300° C. In general, the reac
tion rate increases at the more elevated temperatures.
fact that it is possible to obtain selective cleavage on only
one of the cyclopentadiene groups. It is particularly sur
prising that, in contrast to other reactions of bis-cyclo
cyclic hydrocarbon by-product is materially increased,
best results being obtained from the standpoint of by
pentadienyl metal compounds, the cyclopentadiene group
Moreover, at the elevated temperatures, the yield of the
> . product production at temperatures‘ above about 50° C.
8,080,305
3
4
The process of this invention canlbe, conducted. at sub
The. cyclopentadienyl titanium trichloride product of
atmospheric to superatmospheric pressures. Normally,
this reaction can be used in stoi-chiometric quantities
with triethyl aluminum to form an active catalyst for
it is preferred to conduct the process at atmospheric or
near atmospheric pressures. However, pressures of the
order of 0 to 1000 p.s.i. halogen pressure can be em
ployed.
When solvents are employed, it is best to usea medium
which is- inert to halogenation or which, upon halogena
tion, results in a liquid product.
Very satisfactory re
the polymerization of ole?ns, such as ethylene. Under
normal polymerization conditions, solid polyethylene is
obtained having a melting point of from about 120"--v
130° C.
Example 11
When the procedure of Example I was repeated using
action conditions are obtained in using halogenated hy 10 240 parts of carbon tetrachloride at re?ux conditions,
drocarbons, and preferably highly halogenated hydrocar
5.4 parts of cyclopentadienyl titanium trichloride- and
bons, such as the perhalogen aliphatic compounds or the
higher chlorinated aromatic compounds.
Typical ex
2.6 parts of pentachlorocyclopentane was obtained.
Example III
chloroform, dichloroethanes, tric-hloroethanes, trichloro 15
Example I was repeated except that 320 parts of- car
ethylene, tetrachloroethylene, trichlorobenzenes, tetra
bon tetrachloride were employed as a solvent and the
c-hlorobenzenes, hexachlorobenzene, chlorinated toluenes
reaction was conducted at room temperature. In this
amples of suitable solvents are the carbon tetrachloride,
and xylenes, chlorinated biphenyl, chlorinated naph
thalene and corresponding bromine and ?uorine deriva
tives. In addition to the hydrocarbon solvents, halo
genated ethcrs, such as chlorinated aliphatic ethers, con
taining one to ten carbon atoms, halogenated ethylene
glycol ethers, including polyethers such as halogenated
diethylene glycol diethyl ethers and the like.
The reaction rate of the process can be increased by 25
case, chlorine was bubbled through the reaction mixture
for a period of ten hours. The yield of cyclopentadienyl
'tanium trichloride was 4.6 parts. No pentachlorocyclo
pentane was isolated. Instead, an unidenti?ed oil by~
product was obtained which is [believed to beiaernixture
of chlorinated cyclopentenes.
~
Example IV
the use of catalysts in the reaction. Ultraviolet light- is
A tubular reactor was employed constructed of glass
a particularly useful catalyst for this purpose as well as
which is transparent to ultraviolet light and to this tubular
peroxides, particularly the organic peroxides, such as
reactor was added eight parts of bis(cyclopentadienyl)
lauroyl peroxide, benzoyl peroxide, t-butyl hydroper
titanium dichloride and 160 parts of carbon tetrachloride.
oxide, di-isopropylbenzene monohydroperoxide, acetyl 30 A GE sunlamp was employed to irr-adiate the reactants
peroxide, di-t-butyl peroxide, acetyl benzoyl peroxide,
with ultraviolet light. Gaseous chlorine was passed
succinyl peroxide, peracetic acid, m~bromobenzoyl per
through the reaction vessel for 20 minutes. At the begin
oxide, persuccinic acid, urea peroxide, dialkyl peroxy di
carbonate, asca-ridole, and cyclohexanone peroxide.
ning of the chlorine addition, the reaction mixture was at
room temperature and the temperature rose continuously
The quantity of solvent employed in the process is not 35 during the chlorine addition to a ?nal temperature of 60"
critical except that it is usually best to employ a suf?cient
amount to prevent premature crystallization of the prod
uct, particularly when carrying. out the process in a con
tinuous fashion, or when it is desired‘ to discharge the
reaction to suitable puri?cation and recovery equipment.
In general, it is suitable to employ from about one mole
equivalent to about 100 mole equivalents of solvent.
In carrying out the process of this invention, it is fur
ther desirable to separate the product from the excess
C. The yield of cyclopentadienyl titanium trichloride was
3.0-parts while the yield of pentachlorocyclopentane was
7.44 parts. In addition to greatly increasing" the rate of
reaction to form the desired product, cyclopentadienyl tita
nium trichloride, the ultraviolet light also materially in
creased the formation of pentachlorocyclopentane.
Example V
Example I was repeated except that liquid bromine (30
elemental halogen prior to an unduly long contact period 45 parts) was employed instead of chlorine. In addition, ten
since there is some tendency for the halogen to further
parts of bis(cyclopentadienyl) titanium dichloride were
cleave the remaining cyclopentadienyl group of the prod
employed. The yield of cyclopentadienyl titanium bro
uct. This is much less prevalent with bromine than it is
with chlorine.
mine dichloride (melting point 165°-170° C.) was 9.18
The following are typical examples which illustrate the 50 parts. Fractional crystallization yielded pentabromocyclo
pentane, melting at l02°-103° C.
process of the present invention.
Example VI
Example I
To a reactor equipped with a gaseous halogen inlet
Example I is repeated except that bis(methylcyclopenta
tube having an exit port below the surface of the liquid‘ 55 dienyl) titanium‘ dichloride is employed to produce the
corresponding methylcyclopentadienyl titanium trichlo
reactants was added eight'parts of bis(cyclopentadienyl)
ride. This reaction is conducted in 300 parts of tetra
titanium dichloride and: 300. parts of carbon tetrachlo
chloroethylene at a temperature of 0° C. A good yield
ride. Chlorine gas at atmospheric pressure was passed
of product is obtained.
'
through the mixture at a moderate rate for 2.66 hours
while maintaining the reaction temperature between 55." 60
Example VII
60° C. until the bis(cyclopentadienyl) titanium dichlo
' Example I is repeated except that bis(cyclopentadienyl)
ride was consumed, as was evidenced by the change of
zirconium dichloride is employed, using a reaction tem-v
color of solution from dark red to yellow. Excess chlo
perature of 10° C. Also, the compound is brominated by
time was purged with nitrogen and the reaction mixture
was concentrated by distillation of solvent. After cool 65 feeding liquid bromine t0 the reactor instead of gaseous
chlorine. The reaction is conducted in 200 parts of trie
ing to room temperature, the yellow crystals were ?ltered
chlorobenzene solvent. The cyclopentadienyl zirconium
oil to give 5.6 parts of cyclopentadienyl titanium trichlo
bromide dichloride is obtained in good yield.
ride, melting point 185“ C. (at decomposition)._ The
remaining product was recrystallized from a mixture of
Example VIII
methylene chloride with carbon tetrachloride. The sol 70
vent was distilled under reduced pressure from the car
‘ Example -I is repeated except that bis(ethylcyclopenta
bon tetrachloride. The residue was dissolved in n-pen
dienyl) hafnium di?uoride is reacted with fluorine in 225
tane, ?ltered, and ?ltrate was chilled by Dry Ice. White
parts of chlorinated biphenyl at a temperature of 210° C.
crystals were ?ltered ‘off to give 2.39 parts of pentachloro
The ethylcyclopentadienyl hafnium tri?uoride is .recove
cyclopentane, melting point -39°—4l9 C.
75 ered in accordance with procedure of Example‘ I.
8,080,305
reacted at re?ux in 175 parts of chloroform with gaseous
chlorine to produce in good yields cyclopentadienyl vana
dium trichloride.
Example X
Example I is repeated except that bi-s(?uorenyl) nio
3. The process of claim 1 wherein said solvent is car
bium trichloride is reacted with liquid bromine in carbon
tetrachloride at the re?ux temperature of the solvent. 10
The product obtained in this reaction is ?uorenyl niobium
bromide trichlori-de.
Example XI
Bis(vinylcyclopentad-ienyl) tantalum tri?noride (12
parts) is reacted with ?uorine gas (in excess) in 1,1,1
6
metal trihalide and thereafter recovering said trih-alide
‘from the reaction system.
2. The process of claim 1 wherein said bis(cyclopenta
dienyl) metal dihalide is bis(cyclopent~adienyl) titanium
dichloride and said halogen is chlorine.
Example IX
Bis(cyclopentad-ienyl) vanadium dichloride (7 parts) is
15
trichloroethane at the re?ux temperature of the solvent.
hon tetrachloride.
4. The process of claim 1 wherein said bis(cyclopenta
dienyl) metal dihalide is bis(cyclopentadienyl) titanium
dichloride, said halogen is chlorine and said solvent is
carbon tetrachloride.
5. A process for producing 1a monocyclopentadienyl
metal tetrahalide having the formula
wherein Op is selected from a group consisting of a cyclo
pentadienyl hydrocarbon group and a substituted cyclo~
pentaidienyl hydrocarbon group; M is a metal selected
from a group consisting of niobium, tantalum and molyb
A good yield of vinylcyclopentadienyl tantalum tetra
?uoride is obtained.
Example XII
denum; X is a halide selected from a group consisting of
?uorine, chlorine and bromine; rfrom a bis(cyclopenta
B-is(indenyl) molybdenum trichloride is reacted with
dienyl) metal trihalide having the formula
chlorine in {accordance with the procedure of Example I
in trichloroethylene under re?ux conditions. The indenyl
molybdenum tetrachloride is obtained in excellent yield.
Cp, M and X are as de?ned above, which process
The bis(cyclopentadienyl) metal halides employed as 25 wherein
comprises
reacting said trihalide with a halogen selected
reactants in this invention may be made by conventional
from the group consisting of ?uorine, chlorine and bro
techniques. One suitable method is disclosed, for ex
mine at a temperature of from —50° C. to 300° C. in an
- ample, in J. Am. Chem. Soc., vol. 76, 4179 (1954).
I claim:
inert liquid organic solvent and in the presence of ultra
1. A process for producing a monocyclopentadienyl 30 violet light; so as to produce said monocyclopentadienyl
metal tetrahalide and thereafter recovering said tetrahalide
metal trih-alide having the formula
from the reaction system.
OPMXa
wherein Cp is selected from a group consisting of a cyclo
References Cited in the ?le of this patent
UNITED STATES PATENTS
pentadienyl hydrocarbon group and a substituted cyclo 35
pentadienyl hydrocarbon group; M is a metal selected
from a group consisting of titanium, zirconium, hafnium
2,849,471
2,911,424
Tlhomas _____________ .._ Aug. 26, 1958
Kaufman _____________ __ Nov. 3, 1959
and vanadium; X is 1a halide selected from the group con
2,914,572
Amir .._.._____.. ______ _._ Nov. 24, 1959
sisting of ?uorine, chlorine and bromine; from a b-is(cyclo
2,922,802
2,922,805
Kaufman ___________ __ Jan. 26, 1960
Kaufman ____________ __ Jan. 26, ‘1960
wherein Cp, M and X are as de?ned above, which process
2,948,667
Limido et al. ___.__..____ Aug. 9, 1960
comprises reacting said dih'alide with a halogen selected
from the group consisting of ?uorine, chlorine and bro, 45
1,160,765
France ______________ __ Mar. 10, 1958
pentadienyl) metal dihalide having the formula
40
FOREIGN PATENTS
mine at a temperature of from -50° C. to 300° C. in an
inert liquid organic solvent ‘and in the presence of ultra
violet light; so as to produce said monocyclopentadienyl
OTHER REFERENCES
Nesmeyanov et 'a1.: “Academy of Sciences or the
USSR,” 100, No. 6, pp. 1099-1101, 1955.
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