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Патент USA US3069455

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tates Patent O?tice
Patented Dec. 18, 19%2
in both unleaded and conventional leaded gasolines made
from a wide variety of base stocks. Of the compounds
encompassedby this invention, those containing both lead
and vanadium are preferred as antidetonants because of
Richard D. Gorsich, Eaton Rouge, 1121., assignor to Ethyl
Corporation, New York, NHL, a corporation of Dela
the powerful antiknock effects produced thereby. The
No Drawing. Filled June 23, 1961, Ser. No. 120,15}
‘Ill ‘Claims. {61. Zed-429)
most outstanding 'antiknocks are the dialltyllead cyclo
pcntadienyl vanadium tricarbonyls, especially those com
pounds in which the alkyl groups are methyl or ethyl
This invention relates to and has as its principal ob
or a combination of these.
jects, the provision of novel organo bimetallic compounds
Thus, gasoline fuel compositions containing the novel
wherein one metal is selected from group "IV-A and the
compounds of this invention in amounts suf?cient to in
crease the antiknock rating thereof and, in particular,
other from group lV-B, V-B, or Vl-B of the periodic
system; and the provision of novel methods for the prep~
aration of such compounds; the novel compounds being
of particular use as antilcnoclc agents in motor fuels and
vfor other purposes.
The compositions of this invention are organo bimetal
those containing a dialkyllead cyclopentadienyl vanadium
tricarbonyl, are highly effective fuels for internal com
' bustion engines, the use of which is characterized by
smoothness of engine operation.
That the compounds of this invention are ‘highly ver
satile is shown ‘by the fact that their use as antiknock
lic compounds of the general formula
In this formula R is a cyclopentadienyl or alkyl- or acyl
substituted cyclopentadienyl group containing from 5 to
about 18 carbon atoms, or is an indenyl or fluorenyl
group; R’ is a hydrocarbon group, preferably an alkyl,
aryi, cycloalkyl, arailtyl, alkaryl, or alkenyl radical con
taining from 1 to about 18 carbon atoms; MIV is an
element of group lV-A of the periodic system having
an atomic number from 14 to 82, inclusive, i.e., silicon,
germanium, tin or lead; M is an element of group IV-B,
V-B or Vl-B of the periodic system having an atomic
additives not only involves clear-——i.e., unleaded——fuels
but includes leaded fuels as well, that is, fuels containing
a previously known allcyllead antiknock compounds such
as tetraethyliead or containing a mixture of such alkyllead
compounds. Thus, a liquid hydrocarbon fuel for Otto
cycle engines containing antiknock-increasing amounts
of ‘both a tetraalkyllead compound and a lead-containing
compound of this invention is superior in antiknock
effectiveness to the same fuel containing a like amount
of either of said compounds in the absence of the other.
‘Best results occur when the concentration of the tetra
number from 22 to 74, inclusive, i.e., titanium, zirconium,
hafnium, vanadium, niobium, tantalum, chromium, mo
alizyllead compound is equivalent to from about 0.5 to
6.0 grams of lead per gallon and the concentration of the
carbonyl compound is equivalent to from about 0.01
lybdenum or tungsten; a is 4 when M is a group IV—B
metal and is 3 when M is a group V-B or VI~B metal;
to 4.0‘ grams of lead per gallon.
cause of their economy and availability) are leaded or
The preferred antiknock fuels of the invention (be
when M is a group V-B metal and the sum of b and c
unleaded gasolines containing a compound of the formula
is 4 when M is a group IV-B or Vl-B metal; and d is
2 when M is a group V43» metal and is 1 when M is a
group lV-‘B metal or ‘VI-‘B metal.
40 wherein MIV is tin or lead; R is a cyclopentadienyl or
compositions of this invention are, in general, liq
uid or low-melting solid compounds which are stable at
lower alkyl- or acyl~substituted cyclopentadienyl group,
e.g., methyl cyclopentadienyl or acetyl cyclopentadienyl,
ordinary temperaturesand which can readily be prepared
or is an indenyl or ?uorenyl group, and R’ is a lower
and stored without special precautions for future use.
The lead compounds melt, in general, at lower tempera
tures than the corresponding tin compounds and the melt
ing points tend to increase with the number and molecular
weights of the organic substituents designated above as R’.
alkyl group, e.g., methyl, ethyl, pentyl, etc., or is an aryl
These compounds vary in color from white through
yeliow to orange. The depth of color tends to increase
with the atomic weight of the group IV—A metal and with
the number of the group IV-B, V—B or VI-B metal car
bonyl groups in the molecule.
The compounds of this invention in general are soluble
in organic solvents such as aliphatic and aromatic hydro’
carbons, e.g., n-hexane, petroleum naphtha and benzene,
in alcohols such as ethanol and hexanol, in halohydro
carbons such as methylene dichloride and carbon tetra
., group having up to 8
carbon atoms, e.g., phenyl, tolyl,
Xylyl, etc.
addition to their effectiveness as antiknock agents
for hydrocarbon fuels, the compounds of this invention
are excellent lubricant additives.
In this application, as
well as in fuels, they exhibit unusual versatility. Thus,
when dissolved in lubricants, they effectively improve the
’ ricating properties thereof, greatly reduce engine wear,
virtually eliminate frictional damage, and/ or bring about
overients in stability.
Their versatility is further
a .ested to by the wide variety of natural and synthetic
lubricant bases in which they produce the above effects.
For example, they are highly effective for the above and
other purposes in such lubricating and industrial oils as
chloride, in others such as diethyl ether, methyl ethyl ether
and tetrshydrcftn'an
in mixtures of
Of the metals represented by MW in the above formula,
crankcase lubricating oils, transformer oils, turbine oils,
transmission ?uids, cutting oils, glass annealing oils, gear
lead is preferred for several reasons. It is readily sepa
rated from its ores, is available in large quantities and is
inorganic thickening agents, hydraulic ?uids and, in gen
considerably cheaper than the other metals. Consequent
ly, the lead compounds of the invention are more adapted
for preparation on a larger scale thereby taking advantage
crude petroleum or produced synthetically.
Typical of these synthetic lubricants are the poly
butene oils, the ester oils, the silicone oils, phosphates,
of the economies normally associated with large scale
phosphonates and the like. The ester oils include such
compounds as di-Z-ethylhexyl sebacate, di-sec-amyl-seba
oils, mineral white oils, oils thickened with soaps and
eral, engine and industrial oils which are derived from
The novel compounds of this invention are of value
cate, di-Z-ethylhexyl azelate, di~3-methylbutyl adipate, di
in the chemical and allied arts. For example, the lead 70 Z-ethylhexyl adipate, diisooctyl adipate, di-Z-ethylhexyl
compounds are potent antiknoclc agents and in this utility
they are versatile agents in that they are highly e?ective
phthalate, dibutoxyethyl phthalate, pentaerythritol tetra
caproate, triethylene glycol .di-Z-ethylhexanoate and
polyethylene glycol di-Z-ethylhexanoate.
Examples of
LA metals, sodium and potassium are preferred be
cause of their availability, reactivity, and economy and,
of the group IV—B, V-B and VI-B metals (i.e., M), vana
the silicone oils are the dimethyl, divinyl, diphenyl, meth
yl vinyl, methyl pheuyl, diethyl, dibutyl, di-p‘bromo
phenyl, di-p-chlorophenyl, di-p-?uorophenyl, di-m-tri?uo
romethylphenyl, di-p-phenoxyphenyl, di-m-chlorophenyl,
di-3,4-dichlorophenyl, di-3-chloro-4-bromophenyl, di-p
dium is preferred for the reasons noted above.
The halide reactants are mono-, di- or triorganometal
halide compounds having the formula
methoxyphenyl and di-p-cyanophenyl siloxanes, i.e., sili
cone derivatives.
wherein MIV is silicon, germanium, tin or lead, i.e., an
element of group IV-A of the periodic system having an
atomic number from 14 to 82, inclusive; X is halogen; f
is 1, 2 or 3; and R’ is an alkyl, aryl, cycloalkyl, aralkyl,
alkaryl or alkenyl radical; and wherein the several R’
Among the most effective compounds of this invention
as lubricant additives are those containing vanadium
bonded to lead and particularly to tin. Thus, these are
the preferred lubricant additives for use in accordance
with this invention.
groups can be the same or different.
Generally speak
Accordingly, hydrocarbon lubricant compositions con
taining, in amounts sufficient to improve the lubricating
properties thereof, the novel compounds of this inven
ing, each of the R’ radicals contains up to about 18
carbon atoms. Of the halogens, chlorine is preferred be
tion wherein M is vanadium and Ml‘v is lead or tin and,
cause the organic chlorides of MIV are generally more
stable and more soluble in organic solvents than the
bromides and iodides and are more reactive than the
dienyl vanadium tricarbonyl, are effective lubricants for
internal combustion engines and for other applications. 20 ?uorides. Further, chlorine is the cheapest of the halo
gens and therefore, the organic MTV chlorides are more
An excellent feature of these lubricant additives is that
economical to prepare than any of the other halides.
they can be used not only in a wide variety of oils but
In this process MIv is preferably tin or lead since the
also in combination with other additives without in any
reaction proceeds very smoothly for these metals giving
Way impairing their eifectiveness or that of the other ad
in particular, those containing a dialkyltin cyclopenta
good yields of especially valuable products.
ditives. Such other additives include, for example, anti
oxidants, metal deactivators, detergents-dispersants, pour
point depressants, viscosity index improvers, antifoam
In general, the halide groups of the halogen reactants
are completely replaced by the cyclopentadienyl metal
carbonyl groups of the carbonyl reactant, one cyclo
agents, corrosion inhibitors, oiliness or ?lm strength
pentadienyl metal carbonyl group being present in the
agents, dyes and the like.
The preferred lubricants of the invention are the cheap 30 formula of the product for each halogen atom originally
present in the halogen reactant. The reaction product
and readily available liquid hydrocarbon crankcase lubri
may on occasion he a mixture of mono-, di- and tri
cating oils containing from about 0.05 to about 5.0
substitution products which can readily be separated by
weight percent of vanadium as a compound of the for
solvent extraction, fractionation or other appropriate
wherein MIv is tin or lead, R is a cyclopentadienyl or
in an inert organic solvent.
lower alkyl or acyl cyclopentadienyl group, e.g., methyl~
and consequent ease of separation from the reaction prod
ucts and the ease with which the solvent may be made and
kept anhydrous.
The reaction of this invention proceeds smoothly and
rapidly at moderately elevated temperatures, reaching
vinyl chloride.
completion for the reaction of lower alkyl derivatives of
the group IV-A metal halides with carbonyl reactants
containing an unsubstituted cyclopentadienyl radical-in
15 minutes to a half hour at 50—100° C. Somewhat
longer reaction times are desirable for the higher alkyl
and the substituted cyclopentadienyl derivatives. The
reaction temperature can vary from room temperature
or below to the normal re?ux temperature of the solvent
or even higher if pressure is employed. However, ele
vated temperatures should be used with care since pro
longed heating at reflux may cause some decomposition
of the reaction product. The pressure employed may
The compounds of this invention are best prepared by
reacting an alkali metal derivative of a cyclopentadienyl
or alkyl or acyl cyclopentadienyl carbonyl of a metal of
group IV-B, V—B or VLB of the periodic system (tita
nium, zirconium, hafnium, vanadium, niobium, tantalum,
chromium, molybdenum or tungsten) with an organo
metal halide of a metal of group IV-A of the periodic
system (silicon, germanium, tin or lead). In this reac
tion, the alkali metal of the carbonyl reactant is replaced
by the organometallic radical of the halide reactant. The
carbonyl reactants used in this process are preferably
alkali metal cyclopentadienyl or alkali metal alkyl or
range from 10 millimeters of mercury or less to 100 at
acyl cyclopentadienyl carbonyl compounds of titanium,
zirconium, hafnium, vanadium, niobium, tantalum, chro
mospheres or more, but in general, normal atmospheric
wherein R is a cyclopentadienyl or alkyl or acyl cyclo
pentadienyl group, or is an indenyl or ?uorenyl group,
M is titanium, zirconium, hafnium, vanadium, niobium,
tantalum, chromium, molybdenum or tungsten, i.e., a
Ethers are generally pre~
ferrecl because of their solvent power for the reactants,
and tetrahydrofuran is particularly preferred because of
the ready solubility of the reactants therein, its volatility
cyclopentadienyl or acetylcyclopentadienyl, or is an in
denyl or ?uorenyl group, and R’ is a lower alkyl group,
e.g., methyl, ethyl, pentyl, etc., or is an aryl group having
up to about 8 carbon atoms, e.g., phenyl, tolyl, xylyl, etc.
In addition to the foregoing uses, the compounds of
this invention ?nd application as plasticizers and stabi—
lizers for vinyl and other synthetic resins such as poly
mium, molybdenum or tungsten having the formula
The reaction of this invention is normally carried out
group IV-B, V—B, or VI-B element having an atomic
number of 22 through 74, inclusive (Periodic Chart of
the Elements, Fischer Scienti?c Company, New York,
1957), MI is lithium, sodium, potassium, rubidium or
cesium, i.e., a group I-A element having an atomic num
ber of 3 through 55, inclusive, a is 4 when M is a group
lV-B metal and is 3 when M is a group V-B or VI-B
metal, and e is 2 when M is a group V—B metal and is 1
when M is a group IV-B or VI~B metal. Of the group 75
pressure is wholly satisfactory and preferred.
The invention will be more fully understood by ref
erence to the following set of illustrative examples in
which all parts and percentages are by Weight.
Example I
A solution of 7.9 parts (0.03 mole) of molybdenum
carbonyl, Mo(CO)5, and 3.2 parts (0.036 mole) of cy
clopentadienylsodium in 200 parts of tetrahydrofuran
was re?uxed overnight. To the resulting yellow mixture,
containing the so-formed cyclopentadienyl molybdenum
tricarbonyl sodium, was added 3.6 parts (0.015 mole)
of dimethyltin dichloride. The mixture was briefly heat
ed to re?ux and then the solvent was evaporated in vacuo.
The residue was extracted with methylene dichloride.
The methylene dichloride extract was evaporated and the
residue was recrystallized from a mixture of methylene
dichloride and n-hexane to give 2.6 parts (27 percent)
hour. The product is octadecylrnethylcyclopentadienyl
of large yellow crystals of dimethyltin bis(cyclopentadi
tungsten tricarbonyl triphenyllead.
enylmolybdenum tricarbonyl) ,
[CpivEo(CG)3Snl\/i e2,
melting with decomposition at 155-160° C.
Analysis.—Calculated C 33.84, H. 2.53. Found C
Example XI
10 parts of didodecylcyclopentadienyltitaniurn tetra
carbonyl lithium is added to 4.6 parts of dibenzylsilicon
dibrornide and the mixture is treated ‘with 660 parts of
the diethyl ether of diethyiene glycol. Reaction for 1
hour at 80° ‘C. results in the formation of bis(didodecy1
33.85, H 2.52.
Example 11
When 6.95 parts of potassium methylcyclopentadienyl
titanium tetracarbonyl are reacted with 9.36 parts of
cyclopentadienyltitanium tetracarbonyl) dihenzyl silicon.
triethyllead bromide in 730 parts of benzene at 50° C. 10
Example XII
for a period of 15 minutes, methylcyclopentadienylti
taniurn tetracarbonyl triethyllead is obtained.
Example 111
9.0 parts of methylbutylcyclopentadienylzirconium tet
racarbonyl sodium is reacted With a mixture of 4.6 parts
of phenethylgerrnanium triiodide and 620 parts of the
dihutylether of diethylene glycol. The mixture is heated
rubidium and dibutylsilicon diiodide in the proportion
to 50° C. and maintained at that ‘temperature for 1 hour.
of 9.9 parts of the former to 4.9 parts of the latter are
dissolved in 670 parts of toluene and are reacted at 80°
‘C. for a period of 15 minutes. The product, bis(methyl
Tris(methylbutylcyclopentadienylzirconium tetracarbon
yi) phenethylgermanium is obtained.
Example XIII
ethylcyclopentadienylzirconium tetracarbonyl) dibutyl 20
silicon may be puri?ed by recrystallization from anhy~
Tetrahydrofuran solutions of 11.1 parts of indenylhaf
drous ethanol.
nium tetracarbonyl potassium and 10.7 parts of tri-o
Example‘ I V
tolyltin chloride are mixed and the mixture is dissolved
in 980 parts of tetrahydrofuran. The product is indenyl‘
‘Dimethylcyclopentadienylhafniurn tetracarbonyl cesium
(13.2 parts) and n-octylgermanium trichloride (2.43
hafnium tetracarbonyl tri-o-tolyltin.
parts) are dissolved in 700 parts of o-xylene. The mix
ture‘ is stirred for 15 minutes at 85° C. The product is
tris(dimethylcyclopentadienylhafnium tetracarbonyl) n
Example XI V
A ‘mixture of 7.9 parts of ?uorenylvanadium tricarbon
yl dilithium, 14.4 parts of dixylyllead dibromide and 101
30 parts of benzene is heated to 60° C. for a period of 11/2
Example V
hours. The dimer of iiuorenylvanadium tricarbonyl
dixylyllead is obtained.
Example XV
A mixture ‘of 8.3 parts of acetylcyclopentadienylnio
bium tricarbonyl disodium, 10.3 parts of dicyclopenta
A mixture of 6.75 parts of diethylcyclopentadienyl
Vanadium tricarbonyl dilitnium and 15.4 parts of di-n
dodecyltin dibrornide is dissolved in 1000 parts of mixed
hexancs and heated to re?ux for a half hour. The prod~
not is the dimer of diethylcyclopentadienylvanadium tri~
carbonyl di-n-d'odecyltin.
Example VI
To 8.60 parts of butylcyclopentadienylniobiurn tricar~
bonyl disodium, 22.8 parts of dicetyllead diiodide is
added and the mixture is dissolved in 1410 parts of n
hexene. The solution is heated to reflux for a period of
1 hour. The dimer of butyicyclo-pentadienylniobium tri
carbonyl dicctyllead is obtained.
Example VH
dimer of acetylcyclopentadienylniobium tricarbonyl di
Example XVI
16.5 parts of octadecylcyclopentadienyltantalum tri
car‘oonyl dipotassium is added to a mixture of bis(niethyl
~ cyclopentadienyl)germanium di?uoride (6.7 parts) With
1080 parts of o-xyiene and the mixture is stirred at 70° C.
Dibutylcyelopentadienyltantalum tricarbonyl dipotas
sium, dioctadecylsilicon dichloride, and n-heptane are
combined in the ratio 13:15:1260. The mixture is re
acted at a temperature of 80° C. for a period of 1 hour.
The product is the dimer of dibutylcyclopentadienyl~
entalum tricarhonyl dioctadecylsilicon.
Example VH1
dienylsilicon diiodide and 840 parts of toluene is heated
to 60° C. for a period of 1/2 hour. The product is the
(from chromium hexacarbonyl and octylcyclopentadien
yliithiurn) (8.0 parts) and dicyclohexylgermanium di‘oro
mide (5.0 parts) are dissolved in 590 parts of n-octane.
The mixture is stirred for 1 hour at 80° C. Bis(octyl
cyclopentadienylchromium tricarbouyl) dicyclohexylger
manium is obtained in good yield.
Example IX
When 13 parts or" octadecylcyclopentadienylmolybden
um tricarbonyl sodium and 5 .2 parts of acetylcyclohexyl
-tin triiodide are mixed with 820 parts of petroleum
naphtha and the mixture is heated under reflux for a
for 1 hour. The product is the dimer of octadecylcyclo
pentadienyltantalum tricarbonyl bis(methylcyclopenta~
dienyl) germanium.
Example XVII
5.2 parts of cyciopentadienylchromium tricsrbonyl
lithium is dissolved in 540 parts of mixed hexanes and
the solution is mixed with 6.9 parts or" bis(ethylpropyl~
cyclopentadienyl)tin dibrornide. The mixture is heated
to reflux for a half hour. The product is bis(cyclopenta
dienylchroniium tricarhonyl) bis(ethylpropylcyclopenta
dienyl ) tin.
Example XVIII
When 7.1 parts of rnethylcyclopentadienylmolybdenum
tricarbonyl sodium is reacted with 5.0 parts of methyl
lead triiodide in 540 parts of n-hexane under re?ux [or a
period of 15 minutes tris(methylcyclopentadienylmolyb
denum tricarbonyl) methyllead is obtained.
Example XIX
Ethylcyclopentadienyltungsten tricarbonyl potassium
period of 11/2 hours. tris(octsdecylcyclopentadienyl
and triethylsilicon chloride in the proportion of 10 parts
molybdenum tricarbonyl) acetylcyclohexyltin is obtained‘.
‘of the former to 3.8 parts of the latter are dissolved in
520 parts of methylene dichloride and are reacted at 60°
Example X
To 16 parts of octadecylmethylcyclopentadieny1tungsten tricarbonyl potassium, 12 parts of triphenyllead chloride is added and the mixture is dissolved in 1250 parts
of ether. The resulting mixture is heated to reflux for
C. for a period of 15 minutes.
The product is ethyl
cyclopentadienyltungsten tricarbonyl triethylsilicon.
Example XX
Methylethylcyclopentadienyltitanium tetracarbonyl lith
ium (6.9 parts) and dibutylgermanium di?uoride (2.81
su?icient amount of a base fuel consisting of 15 percent
by volume of alkyiate gasoline and 85 percent of cata
lytically cracked gasoline to give a lead concentration of
parts) are dissolved in 500 parts of n-octane. The mix
ture is stirred for a half hour at 60° C. The product
is bis(methylethylcyclopentadienyltitanium tetracarbonyl)
Example XXI
1.25 grams of lead per gallon. The addition to this
blended fuel of 0.16 gram of titanium per gallon as ethyl
cyclopentadienyltitanium tetracarbonyl trimethyltin in
8.0 parts of dimethylcyclopentadienylzirconium tetra
carbonyl sodium and 5.1 parts of n-octyltin triiodide dis
creases the antiknock value thereof.
The following examples serve to illustrate the antiwear
utility of the compounds of this invention. All per
solved in 590 parts of petroleum naphtha are heated under
re?ux for 1 hour. The product is tris(dirnethylcyclo—
centages given in these examples are by ‘weight.
Example XXIX
pentadienylzirconium tetracarbonyl) octyltin.
Example XXII
A mixture of 11.3 parts of diethylcyclopentadienyl
hafnium tetracarbonyl potassium and 15.6 parts of tri~a~
naphthyllead chloride is dissolved in 1210 parts of di
ethyl ether and heated under re?ux for one and one
quarter hours. The product is diethylcyclopentadienyl
hafnium tetracarbonyl tri-a-naphthyllead.
Example XXIII
To 6.8 parts of butylcyclopentadienylvanadium tri
carbonyl dilithium, 6.8 parts of diallylsilicon dibromide
are added and the mixture is dissolved in 610 parts of the
diethyl ether of diethylene glycol.
. stirred for a half hour at 60° C.
The solution is
The dimer of butyl
cyclopentadienylvanadium tricarbonyl diallylsilicon is ob
tained in good yield.
Example XXIV
A Mid-Continent solvent-extracted mineral oil not
containing an additive of the invention is run in a 4-ball
15 Wear machine using 1/2 inch SAE 52~l00 steel balls, a
speed of 570
for 2 hours and a load of 10 kilo
grams. Following the test, the balls are disassembled
and the average scar diameter on the lower three balls is
measured. The test is then repeated with the addition
to the mineral oil of 2 percent by weight of methylcyclo
pentadienylvanadium tricarbonyl dioctyltin (dimer); the
average scar diameter in the second case is less than in
the ?rst.
Example XXX
To the Mid-Continent oil of Example XXIX is added
1.5 percent of bis(cyclopentadienyltitanium tetracarbonyl)
This addition results in a marked diminu
tion in wear as tested by the 4-ball Wear machine.
As indicated above, a wide variety of organo bimetallic
compounds fall within the scope of this invention. Ex
Octylcyclopentadienylniobium tricarbonyl disodium, di
vinylgermanium ?uoride and the dibutyl ether of diethyl
ene glycol are combined in the ratio ‘102412880. The
amples of these compounds are the following: cyclopenta
mixture is reacted at a temperature of 60° C. for a
nium, dimer of butylisooctylcyclopentadienylnobium tri
period of a half hour.
The product is the dimer of
octylcyclopentadienylniobium tricarbonyl divinylgermani
dienyltitaniurn tetracarbonyl trimethylsilicon, bis(methyl
cyclopentadienyltungsten tricarbonyl)
carbonyl bis-2,4-xylyltin, tris(diethylcyclopentadienylzir
conium tetracarbonyl) cyclohexyllead, dimer of ?uorenyl
vanadium tricarbonyl dimesitylsilicon, indenylchromium
tricarbonyl triisobutylgermanium, bis(methylpropylcyclo
Example XXV
tetracarbonyl) dicetyltin, dimer of
When 15.8 parts of cetylcyclopentadienyltantalum tri 40 pentadienylhafnium
tricarbonyl ditolyllead, tris(vi
carbonyl dipotassium and 10.7 parts of dimesityltin di
nylcyclopentadienylrnolybdenum tricarbonyl) vinylsilicon,
chloride are mixed with 1190 parts of tetrahydrofuran
and the mixture is heated under re?ux for 1 hour, the
dimer of cetylcyclopentadienyltantalum tricarbonyl di
mesityltin is obtained in good yield.
As stated above, the compounds of this invention are '
extremely useful as antiknock agents for internal combus
tion engine fuels. The following speci?c examples serve
to illustrate the antiknock use of the said compounds.
Example XXVI
A base stock is prepared by mixing 24 volumes of iso~
pentane, 66 volumes of isooctane and 10 volumes of
cumene. To this base stock is added 0.75 gram of
lead per gallon as a mixture (296.0 parts) containing
5.5 percent of tetramethyllead, 24 percent of trimethyL
ethyllead, 37.5 percent of dimethyldiethyllead, 26 per
cent of methyltriethyllead and 7 percent of tetraethyl
lead. To the resulting mixture are added 79.1 parts (0.70
theory) of 1,2-dichloropropane and 145.6 parts (0.775
theory) of ethylene dibromide. Finally, 0.15 gram of
molybdenum per gallon as bis(cyclopentadienylmolyb
denum tricarbonyl) dimethyltin is added. A signi?cant
increase in knock rating accompanies the ?nal addition.
Example XX VII
When the base stock of Example XXVI is treated with
isobutylcyclopentadienyltitanium tetracarbonyl tri-n-octyl
germanium, bis(isopropylcyclopentadienylchromium tri
carbonyl) dicyclopentyllead, bis(butylisooctylcyclopenta
dienylzirconium tetracar‘oonyl) diethylsilicon, dimer of
hexylcyclopentadienylniobium tricarbonyl diphenylgerma
nium, cyclopentadienylhafnium tetracarbonyl triphenyl—
ead, dimer of methylethylcyclopentadienyltantalum tri
carbonyl divinylsilicon, and tris(?uorenyltungsten tricar
bonyl) cyclohexylgermanium. Of the foregoing com
pounds, those wherein the group IV-A metal is lead or
tin, the group V-B metal is vanadium and the organo
radical is cyclopentadienyl or' indenyl or a substitution
product thereof are preferred because of their ease of
preparation and because of their high effectiveness as
antiknock and antiwear agents.
Particularly preferred
compounds, for the reasons given above, include the
dimer of indenylvanadium tricarbonyl diallyltin, methyl
isooctylcyclopentadienylmolybdenum tricarbonyl triocta
decyltin and bis(methylcyclopentadienyltitanium tetra
carbonyl) diphenyllead.
‘In making the valuable compounds of this invention, a
wide variety of reactants are available. The alkali metal
simple or substituted cyclopentadienyltitanium (or other
group IV—B, V-B or VI—B metal) carbonyl is made by
the reaction of the appropriate inorganic metal carbonyl
1.2 grams of vanadium per gallon as the dimer of di—
with the cyclopentadienyl alkali metal compound in tetra
ethylcyclopentadienylvanadium tricarbonyl didodecyltin,
hydrofuran or other suitable solvent. The mixture is
heated to re?ux until the reaction is essentially com~
plete. The reaction mixture is then used without further
treatment for the reaction of the invention. Illustrative
an increase in knock rating is observed.
Example XX VIII
A‘tetraethyllead ?uid is prepared by mixing 323.5 parts
of tetraethyllead with 144.8 parts (0.60 theory) of n
hexyl chloride and 156.2 parts (0.625 theory) of mixed
dibromotoluenes. The resulting ?uid is mixed with a
of these compounds are cyclopentadienylrnolybdenum tri
carbonyl lithium, dibutylcyclopentadienyltantalum tricar
bonyl disodium, ?uorenyltitanium tetracarbonyl potas
sium, methylethylcyclopentadienylchromium tricarbonyl
rubidium and octylcyclopentadienylzirconiurn tetracar
bonyl cesium.
Methods for the preparation of organometal halides——
in either the aliphatic or aromatic portion of the molecule.
These scavengers may also be carbon-, hydrogen- and
oxygen-containing compounds such as haloallryl ethers,
halohydrins, halonitro compounds and the like.
the other reactants in the process of this inveutionware
described by E. Krause and A. von Grosse illtiDl? Chemie
der MetalLOrganischen Verbindungen,” Borntraeger,
Berlin, 1937. Examples of such compounds include tri
phenyltin chloride, dimethyltin dichloride, triphenyllead
chloride, diethyllead dichloride, dimethylsilicon di?uoride,
tris(ethylcyclopentadienyl)silicon iodide, bis(dodecyl
cyclopentadienyl) germanium dibromide, bis(ethylphen
1,668,022; 2,398,281; 2,479,900; 2,479,901; 2,479,902;
2,479,903; 2,496,983; 2,661,379; 2,822,252; 2,849,302;
2,849,303 and 2,849,304. Mixtures of different scaven
Concentrations of organic halide
scavengers ranging from about 0.2 to about 2.5 theories
based on the lead are usually sufficient although greater
or lesser amounts may be used. Thus, in general, use is
made of an amount of organic halide scavenger that is
capable of reacting with the lead during engine com
bustion to form relatively volatile lead halide and thereby
effectively control the amount of deposit formed in the
10 gers may also be used.
yl)tin dichloride, and bis(acetylcyclohexyl)lead di
The reactants-RM(CO),MIe and R’4_fl‘\/l1VXf-used in
the preparation of the compounds of this invention can
be employed in proportions ranging from a 100 percent
or greater excess of the group IV—B, V—B, or V'I—B com
pound to a 100 percent or greater excess of the group
lV-A halide compound. Usually, they are employed in
proportions corresponding approximately to stoichio
metric equivalents but a moderate excess of one- reactant
or the other is oftenused to bring about an increased
reaction rate.
Among the criteria for the choice of solvents to be em
ployed in the reactions of this invention are that the
solvents be liquid under the reaction conditions and that '
they be inert to both reactants and products.
other examples of scavengers that may be used in this
invention are illustrated in U.S. Patents 1,592,954;
ingly, the solvents may include, in general, aromatic hy
drocarbons such as benzene, toluene, the Xylenes and the
like, aliphatic hydrocarbons such as hexanes, heptanes,
octanes, petroleum naphtha and the like, aliphatic or
aromatic others such as dietbyl ether, diethylene glycol
diethyl ether, diethylene glycol dibutyl ether or tetra~
hydrofuran, aliphatic alcohols such as methanol, ethanol,
isopropanol, the pentanols, etc., and halohydrocarbons
such as methylene chloride and carbon tetrachloride, and
the like. The preferred solvent is tetrahydrofuran be
cause of its relatively high solubility for the reactants
and for the other reasons mentioned above.
The reaction of this invention may be carried out at
any temperature Within the normal liquid range of the
solvent or at higher temperatures if tLB liquid phase is
maintained by the application of pressure. The normal
re?ux temperature is perfectly satisfactory in most in
stances but care should be taken not to employ too high
The fuels of this invention can contain other additives.
Typical of these are antioxidants (e.g., N,N'-di-sec-butyl
p~phenylenediamine; p-N-butylaminophenol; 4-methyl-2,
6-di-tert-butyl-phenol; etc.), metal deactivators (e.g.,
N,N'-disalicilideue-1,2-diaminopropane, etc.), dyes, phos
phorus additives (e.g., tri(/3—chloropropyl)thionophos~
phate, dimethyltolylphosphate, dimethyl-xylylphosphate,
phenyldimethylphosphate, tricresylphosphate, phenyldi~
cresylphosphate, cresyldiphenylphosphate, trimethylphos
phate, etc.), boron additives, corrosion inhibitors, deter
gents, antiicing additives, other antiknock agents (e.g.,
methylcyclopentadienylmanganese \tricarbonyl, cyclopen
tadienylmanganese tricarbonyl, cyclopentadienylnickel
nitrosyl, manganese pentacarbonyl, iron carbonyl, dicy
clopentadienyliron, etc.), induction system cleanliness
additives, top cylinder lubricants and the like.
Having thus described the process and novel products
05 this invention it is not intended that it be limited ex
cept as set forth in the following claims.
I claim:
1. A compound represented by the general formula
wherein R is a radical selected from the group consisting
of cyclopentadienyl, alkylcyclopentadienyl and acylcyclo~
pentadienyl radicals containing from 5 to about 18 carbon
45 atoms, and of indenyl and ?uorenyl radicals; R’ is a radi~
a temperature for too long a time inasmuch as excessive
cal selected from the group consisting of allryl, aryl, cy
temperatures may cause more or less extensive decompo
cloalkyl, aralkyl, alkaryl and alkenyl radicals containing
sition of the products. Thus, temperatures in the range
1 to about 18 carbon atoms; M is an element se
of 0 to 200° C. are employable, although best results
lected from the group consisting of the elements of group
are obtained between 50 and 100° C., and this range is
IV—B of the periodic system having atomic numbers
therefore preferred.
from 22 to 72, inclusive, the elements of group V-B of
Because the reaction usually proceeds rapidly under
the periodic system having atomic numbers from 23 to
re?ux at normal pressure, atmospheric pressure is usually
73, inclusive, and the elements of group VI-B of the
satisfactory but pressures ranging from 10 millimeters
periodic system having atomic numbers from 24 to 74,
of mercury to 100 atmospheres may be used if desired.
inclusive; MIv is an element of group ‘IV-A of the peri
The reaction of this invention may be carried out under
odic system having an atomic number from 14 to 82,
any atmosphere inert to both reactants and products.
inclusive; :2 is 3 when M is an element selected from the
The lead and tin compounds are stable on exposure to
group consisting of the elements of groups V-B and VLB
dry air which can thus be used with safety. The use of
the periodic system and is 4 when M is an element
dry nitrogen is preferred for the less stable germanium
and silicon compounds. Other suitable protective atmos 60 of group lV-B of the periodic system; b is an integer
from 1 to 3, inclusive, c is an integer from 1 to 3, in
pheres include gaseous saturated hydrocarbons such as
clusive; the sum of b and c is 4 when M is an element
methane and ethane and the noble gases, helium, neon,
selected from the group consisting of the elements of
argon, krypton and xenon.
groups IV~B and VI-B of the periodic system; the sum
The normally solid compounds of this invention are
of 2b and c is 4 when M is an element of group V-B of
soluble in and can be puri?ed by recrystallization from a
variety of organic solvents. Speci?cally, simple aromatic
solvents such as benzene or toluene, simple aliphatic
solvents such as hexane, alcohols such as ethanol and
halohydrocarbons such as methylene chloride, and their
mixtures, are found to be satisfactory.
In the improved fuels of this invention, organic halide
scavengers can be employed. These scavengers can be
either aliphatic or aromatic halohydrocarbons or a com
bination of the two having halogen attached to carbon 75
the periodic system; and a.’ is 2 when M is an element of A
group V-B of the periodic system and is 1 when M is an
element selected from the group consisting of the ele
ments of groups IV—B and VI-B of the periodic system.
2. The compound of claim 1, wherein MIV is tin.
3. The compound of claim 1, wherein MW is tin and
M is molybdenum.
4. Dimethyltin bis(cyclopentadienylmolybdenum tri
5. The method of preparing the compounds of claim 1
1. 1.
. .2.
which comprises reacting a compound represented by the
general formula
6. The method of claim , wherein MI is sodium and
X is chlorine.
7. The method of claim 5, wherein MIv is tin.
8. The method of claim 5, wherein MTV is tin and M
wherein a is 3 when M is an element selected from the 5 is molybdenum.
group consisting of the elements of groups V-—B and VI-B
9. The method of claim 5, wherein the reaction is car
of the periodic system and is 4 when M is an element of
ried out in an essentially inert organic solvent.
group ‘IV-B of the periodic system, MI is a metal of group
10. The method of claim 5, wherein the reaction is
I-A of the periodic system, e is 1 when M is an element
carried out in an ether as solvent.
selected from the group consisting of the elements of 10
1]. The method of claim 5, wherein the reaction is
groups IV-B and VI—B of the periodic system, and is 2
carried out in tetrahydrofuran as solvent.
when M is an element of group V-B of the periodic
References Cited in the ?le of this patent
system, and R is a radical selected from the group con
sisting of cyclopentadienyl, alkycyclopentadienyl and acyl
cyclopentadienyl radicals containing from 5 to about 18
Closson et al ___________ __ Nov. 7, 1961
carbon atoms, and of idenyl and ?uorenyl radicals, with 15 3,097,953
a compound represented by the general formula
Kozikowski ____________ __ I an. 2, 1962
King et al.: “Chem. and Industry,” pp. 747-748 (June
group consisting of alkyl, aryl, cycloalkyl, aralkyl, alkaryl 20 3.1961).
and alkenyl radicals containing from 1 to about 18 carbon
atoms, and f is an integer from 1 to 3, inclusive.
wherein X is a halogen, R’ is a radical selected from the
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