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Патент USA US3042703

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United States Patent O?lice
3,042,693
Patented July 3, 1962
7.
2
matic compoundshaving from 6 to 18 carbon atoms are
3,042,693
No Drawing. Filed Oct. 18, 1957, Ser. No. 690,90
generally preferred in compounds of this invention. Ben
zene itself, mesitylene, toluene, biphenyl, tetralin, m
hexylbiphenyl, and the like are examples of applicable
aromatic compounds.
Typical examples of other compounds which are also
4 Claims. (Cl. 260-429)
suitable and which do not have an isolated benzene nucleus
ORGANDMETALLHC CGR/EQUNDS
Thomas H. (In?eld, Farmington, and Rex D. Closson,
Northville, Mich, assignors to Ethyl Corporation, New
York, N.Y., a corporation of Delaware
'
-
are styrene cyanomanganese dicarbonyl, methylstyrene
This invention relates to novel organometallic com
cyanomanganese dicarbonyl, naphthalene cyanomanga»
pounds and more particularly to aromatic compounds of 10 nese dicarbonyl, and the like.
manganese. In addition, the present invention relates to
The compounds of this invention can be prepared by a
manufacture and use of the above compounds.
number of techniques. One typical method is to form
It is an object of this invention to provide a new class
of organometallic compounds. More particularly, it is an
object to provide new compounds of manganese which are 15
the desired compound by decarbonylating the correspond
ing aromatic metal tricarbonyl cyanide by pyrolysis in ac
cordance with the following equation
relatively stable and which are soluble in organic media,
particularly hydrocarbons. Another object is to provide
compounds of the above type which are useful as anti
knocks in gasoline used for internal combustion engines.
wherein'A is an aromatic molecule as de?ned above.
Still another object is to provide a novel process for manu 20 This pyrolysis can be conducted at a temperature of be
facture of such compounds and fuel compositions con
tween about 20" and 300° C., but is usually carried out
taining the same. Other objects and advantages of this
between about 50° and 200° C. Likewise, while not
invention will be more apparent from the following de
essential, the reaction is best conducted in an inert liquid
scription and appended claims.
The above and other objects of this invention are ac
medium and preferably in a solvent for‘the tricarbonyl
25 reactant but which is not a solvent for the product. For
complished by the provision of a novel class of compounds
this reason, polar solvents are frequently preferred.
The pyrolysis to form the aromatic cyanomanganese
dicarbonyl can be accomplished simultaneously with the
formation of the aromatic manganese tricarbonyl cyanide
reactant. For example, a typical method for producing
the aromatic manganese tricarbonyl cyanide involves the
having an aromatic molecule coordinated with a manga
nese atom, the compound being stabilized by additional
coordination with two carbonyl groups and a cyano group,
the aromatic molecule contributing six electrons, the car
bonyl groups each contributing two electrons and the
cyano group contributing one electron to the manganese,
reaction of an aromatic manganese tricarbonyl halide
thereby giving the manganese a total of eleven additional
with an active cyanide compound. This reaction can be
electrons and resulting in the manganese atom having the
conducted at temperatures de?ned above for pyrolysis,
con?guration of krypton. More speci?cally, the aro 35 i.e., 20~300° C., to simultaneously produce the com
matic cyano manganese dicarbonyl compounds of this in
pounds of this invention. Likewise, the aromatic man
vention have the general formula
ganese tricarbonyl halide does not require isolation prior
to conversion to the compounds of the present invention.
A typical series of reactions which can be conducted to
wherein A is an aromatic molecule.
40 form the aromatic manganese tricarbonyl cyanide reac
tant is as follows:
The compounds of this invention are unexpectedly
stable to light, heat and other in?uences. As such, these
compounds are very useful in many applications wherein
stability is an important factor. The compounds are also 45
coordination complexes and thus are soluble in organic
media, particularly of the hydrocarbon type. These com
pounds are also antiknocks and, in use, are preferably
injected into internal combustion engines as a component
of the vfuel mixture.
.50
Typical examples of compounds of this invention are
benzene cyanomanganese dicarbonyl, toluene cyanoman
wherein X is a halogen, M is a metal and m is the valence
of the metal M. Thus, the above reactions can be con
ducted separately and, in each instance, the desired inter
mediate separated and isolated. Alternatively, the reac
tions can be conducted simultaneously or sequentially
without separation of products.
.
ganese dicarbonyl, o-xylene cyanomanganese dicarbonyl,
p-xylene cyanomanganese dicarbonyl, mesitylene cyano
The halogenation of the manganese pentacarbonyl (2)
manganese dicarbonyl, diphenyl cyanomanganese dicar 55 can be conducted over a wide temperature range such,
bonyl, tetralin cyanomanganese dicarbonyl, ethylbenzene
cyanomanganese dicarbonyl, n-octyl benzene cyanoman
ganese dicarbonyl, and the like.
The aromatic compounds coordinated to the metal in
the compounds of this invention which are represented by
A in the above formula are‘in general compounds prefer
ably containing an isolated benzene nucleus. That is, aro
matic compounds which are free of aliphatic unsaturation
on a carbon atom adjacent the benzene ring and which
for example, as —70° to 100° C. although the reaction is
preferably conducted at a temperature of 0° to 50° C.
The reaction is preferably conducted in an inert liquid,
preferably one which is a solvent for the manganese
pentacarbonyl, for example, chlorinated hydrocarbons
such as ethyl chloride and carbon tetrachloride, and the
like; aliphatic hydrocarbons such as pentane and hexane;
aromatic solvents such as benzene, toluene and xylene;
solvents such as carbon disul?de and organic acids such
do not contain unsaturation on a carbon atom of a fused
as an acetic acid.
ring which is adjacent the benzene nucleus. That is, the
aromatic compounds which are preferred for this invention
have no aliphatic double bond in conjugated relationship
to the ring. Thus, aryl and alkyl substituted aromatic
critical as long as there is enough to provide solubility for
The concentration of solvent is not
manganese carbonyl.
Any of the halides are suitable in this reaction such as,
for example, the chlorides, bromides, iodides or ?uorides.
compounds are also preferred as are fused ring compounds 70 The reaction of the aromatic compound with the halo
having isolated benzene nuclei, that is, having no unsatura
gen manganese pentacarbonyl (3) is generally catalyzed
tion on a carbon atom adjacent to a benzene ring. .Aro
by a Friedel-Crafts catalyst and is normally conducted
3,042,693
4 .
.
sis of the product was as follows:
preferred temperature range is in the order of 50° to
200° C.
e
manganese dicarbonyl was 170—172° C. Chemical analy
I at a. temperature of from about 20° to 300° C. ‘A more
"
Bya Friedel-Crafts catalyst is meant a. salt having elec-'
Found
Calculated
trophilic characteristics. . These are. usually" halides of
metals of groups IIA, IIB, HIA, IVBLVB, VI-B, VIIB
and VIII of the periodic table. The preferred halides
Carbon ______________________________ _-
' 55. 8
Hydrogen
Nitrogen _____________________________ __
56. 0
. 4. 79
4. 65
5. 45
5. 45
are halides of groups lIIA, IVB and VVIH. Illustrative
examples of preferred metal halides'are boron tn'?uoride,
boron trichloride, boron tribromide, boron triiodide, alu
minum trichloride, aluminum tri?uoride, titanium tetra
An infrared spectrum con?rmed the structure of this prod
10 uct.
The product obtained in this example is an effec
tive antiknock when used in fuels for internal combustion
chloride, titanium tetrabromide, ferric chloride, and the
like. Also in many instances,it is desirable to employ
the corresponding hydrohalide along with the metal hal
ide, e.g. Val-boron trichloride-hydrogen chloride catalyst
engines.
’
'
'
.
"
‘
Example II ,
Mesitylene manganese tricarbonyl iodide (3.86 parts)
15
7 was reacted with 2 parts of potassium cyanide, but in this
system. Other examples of suitable Friedel-Crafts cat
alysts of generally lesser activity are .zinc, gallium, indium,
example the iodide compound Was‘dissolved'in 150 parts
of ice-cold water. A white precipitate was ‘formed im
mediately which was thereafter, ?ltered and washed with
.chromium, manganese and cobalthalides.
The Friedel-Crafts reaction’ (3) is preferably carried 20 ethyl ether; This White preceipitate, mesitylene man
thallium, beryllium, magnesium, zirconium, vanadium,
ganese tricarbonyl cyanide, (2.45 parts) was analyzed by
out in a liquid medium consisting primarily of the aro
chemical analysis and .by infraredv analysis. F This product
was thereafter re?uxed under nitrogen, resulting in the
matic compound Which is reacted with the halogenman
ganese pentacarbonyl. Thus, if it is ‘desired to make the
evolution of carbon monoxide.
‘ benzene manganese .tricarbonyl, the react-ion is conducted
Upon‘ cooling, yellow
in .a benzenem'edium- The reaction can. also be con 25 crystals separated which were thereafter recrystallized
from water. These yellow crystals were mesitylene cyano
' ducted in a halogenated benzene such as'chlorobenzene
rnanganese dicarbonyl havinga melting point of 171
or bromoben'zene, inwhich event the chloroaromatic or
'
bromoaromatic manganese .tricarbonyl-halide .is formed. '
172° C. Thisrproduct
Other substituted aromatic compounds can be‘produced
acteristic infrared spectrum.
in like manner.
.
.
a
.
30
a
also analyzed and'gave char
.
.
Example _III
In addition to the aromatic compound,.other solvents or x
Twenty¢?ve parts of bromomanganese pentacarbonyl,
diluents can be employed. , Typical examples of such
diluents are nitrobenzene; straight chain hydrocarbons
410 parts of aluminum chloride and 108 parts of mesity
‘such .as pentane, hexane, decane, and the like. These
diluents can be used in concentrations of from 0.01 to
100 parts per part of the aromatic compound.
7
Reaction of the aromatic manganese tricarbonyl halide
lene ‘were re?uxedunder nitrogen until the gas evolution
P had terminated. After cooling the reaction mixture, the
mesitylene manganese tricarbonyl bromide was hydro
lyzed 'with 100 parts of water. The water vlayer was
thereafter ‘separated . and treated with excess'potassium
cyanide; A'green precipitatejwas formed. _ Thereafter
with an active cyanide compound (4) is best conducted
attemper'atures of from‘—30° to 250° C.
Most pre
ferredoperation employs temperatures of- above 50° C.
40
suf?cient sodium hydroxide (5 percent solution) was
added to the reaction product to raise the pH to 8.5, un
der which conditions the color of the solution changed
to yellow. The product'was then extracted with water
and below about200° -.C. At the more elevated temper-a
tur'es', the aromatic manganese tricarbonylcyanide de
composes immediately to therdesired aromatic manganese
dicarbonyl cyanide. ' In this process, any active’ cyanide’
’ and the extract was concentrated whereupon yellow crys
compound can be used but the cyanides of metals‘of 45 tals of mesitylene cyanomanganese dicarbonyl were ob
groups I to III of the periodic‘ table are preferred. Best
results are obtained with the alkali metal compounds, such
tained. This product was ‘thereafter recrystallized from
as sodium‘ cyanide, potassium cyanide and lithium cya
nide. Other typical examples of suitable metal cyanide '
carbonyl. The productwas identi?ed by infrared analy
compounds are calcium cyanide, magnesium cyanide
aluminum cyanide.
_
'
l
l'
water giving’6.1‘2 parts of mesitylene'cyanomanganese di
and
V
SIS.
I
Any of a wide variety of solvents can-be employed in
Step 4, particularly polar solvents.’ Water, lower aliphatic
Example IV '
55.
atoms ‘give excellent results. . The concentration of soil
vent isnot critical. Quantities of from about 0.I part to
' about 100 parts per part of reactant can be used, although
' from about 1 ‘to 10 parts are preferred.
.
'
"The following are typical examples which illustrate the
60
present invention and in whichla-ll parts are give'u'by
v
> weight.
. Mesiltylene manganese 'tricarbonyl iodide, (3.86" parts)
65
3 parts of potassium cyanide‘were added.‘ Mesitylene'
cyanomanganese' dicarbonyl, a yellow precipitate, was
formed’directly,'carbon monoxide being evolved’ in about
one mole equivalent quantities. The reaction mixture 70
uct was recrystallized in water three, times, washed with a.
7
Example I is repeated using xylene manganese tricar
bonyl chloride in ethylene glycol solvent to produce
. Example I
was dissolved in 100 parts of hot water and, while boiling,
Example I is repeated except that benzene manganese
tricarbonyl bromide is reacted with sodium cyanide in
1570 parts of ethyl alcohol. The solution isre?uxed until
gas evolution ceases. Similar results are obtained except
that the product is benzene cyanomanganese dicarbonyl.
Example V ll '
'
was cooled and ?ltered and 2.26 parts‘of mesitylene cyano
manganese dicarbonyl product was obtained. This prod
,
. tained.
alcohols .and others ‘such as acetone are preferred. The
alcohols havingalkyl groups containing} to 6 carbon
r
'When the aboveexample is carried out in using other
Friedel-Crafts catalyst such ‘as boron tri?uoride, boron
trichloride-HCI and ferric'chloride' similar results‘are ob
xylene cyanomanganese dicarbonyl. The pyrolysisreac
tion is conducted at: 100°C. until‘all of the freed carbon
monoxide has been evolved. - '
‘
‘
Example VI
_ Tetralin manganese ltricarbonyl‘ iodide (4.4 parts) is
dissolved in 120 parts of water, This solution is heated
to a temperature of50° C. and 3.2’ parts of calcium cya
nide is added over a period ‘of 10 minutes. The heating
is continued withstirring until there is no evidence of fur
smallramount of diethyl ether andrdried under reduced
pressurei The meltingv point of the mesitylene cyano- 75 ther gas evolution. .The product reaction mass is then
3,042,698
5
. 6
cooled to room temperature and the tetralin cyanoman
I
words, a theory of halogen represents two atoms of halo
ganese dicarbonyl puri?ed as in Example 1.
Example VII
gen for every atom of lead and/or manganese present.
In like manner, a theory of phosphorus is the amount of
phosphorus required to convert the lead present to lead
Ethylbenzene manganese tricarbonyl cyanide is heated
orthophosphate, Pb3(PO4)2, that is, a theory of phos
in dioxane to a temperature of 100° C. The solution is
maintained at this temperature until the gas evolution
ceased. The reaction mixture is then cooled to room
phorus based on lead represents an atom ratio of two
atoms of phosphorus to three atoms of lead. When
based on manganese, a theory of phosphorus likewise
represents two atoms of phosphorus for every three atoms
temperature and the product ethylbenzene cyanomanga
nese dicarbonyl is recovered in accordance with the pre
ceding examples.
10 of manganese, that is, su?icient phosphorus to convert
manganese to manganese orthophosphate, Mn3(PO4)2.
When employing the compounds of this invention to
gether with scavengers, an antiknock ?uid for addition
to hydrocarbon fuels is prepared comprising aromatic
Example VIII
Triethylbenzene manganese tricarbonyl chloride (8.3
parts) is dissolved in 250 parts of acetone. The solu
tion is heated to a rolling boil and 5 parts of lithium 15 cyanomanganese dicarbonyl compounds together with
various halogen-containing organic compounds having
cyanide is added to the solution. Carbon monoxide gas
from 2 to about 20 carbon atoms in such relative pro
is evolved and the solution is maintained at re?ux until
portions that the atom ratio of manganese-to-halogen is
no additional gas evolution is apparent. The triethyl
from about 50:1 to about 1:12. The scavenger com
benzene cyanomanganese dicarbonyl is recrystallized
from triethanol amine and subsequently recrystallized 20 pounds can be halohydrocarbons both aliphatic and aro
matic in nature, .or a combination of the two, with line
twice in water. The crystals are washed with a small
gens being attached to carbons either in the aliphatic or
amount of dimethyl ether and dried at reduced pressure.
the aromatic portions of the molecule. The scavenger
Example IX
compounds may also be carbon, hydrogen, and oxygen
Fifty parts of bromomanganese pentacarbonyl, 18 25 containing compounds, such as haloalkyl others, halo~
hydrins, halo esters, halonitro compounds, and the like.
parts of aluminum bromide and 200 parts of n-cctyl
Still other examples of scavengers that may be used in
benzene are re?uxed in an inert atmosphere until gas
conjunction with our manganese compounds either with
evolution has ceased. After cooling the reaction mix
ture, the product is hydrolyzed with 150 parts of water. 30 or without hydrocarbolead compounds are illustrated in
The water layer is separated and 4 parts of sodium
U.S. Patents 2,398,281, 2,479,900, 2,479,901, 2,479,902,
cyanide is added to this solution. Su?icient potassium
and 2,479,903, and the like. Mixtures of different
scavengers may also be used. These fluids'can contain
hydroxide (10 percent solution) is added to the reaction
product to raise the pH of the solution to 8.0.
The
other components as stated hereinabove.
In like man
product, n-octylbenzene cyanornanganese dicarbonyl, is 35 ner, manganese-containing ?uids are prepared contain
ing from 0.01 to 1.5 theories of phosphorus in the form
thereafter recovered in accordance with the procedure
of phosphorus compounds.
of Example III.
The compounds of this invention can be employed
with hydrocarbon fuels and lubricating oils for improv
ing operating characteristics of spark ignition internal
combustion engines. The compounds can be used in
fuels and lubricating oils by themselves or together with
other additive components, such as scavengers, deposit
To make up the ?nished
fuels, the concentrated ?uids are added to the hydro
carbon fuel in the desired amounts and the homogeneous
40
?uid obtained by mixing, agitation, etc.
The ratio of the weight of manganese to lead in ?uids
and fuels containing the two components can vary from
about 1:880 to about 50:1. When no lead is present,
modifying agents containing phosphorus and/or boron,
the latter ?gure becomes 1:0. A preferred range of
ratios, however, when both the manganese compounds of
and also other antiknock agents, such as tetraethyl
this invention and hydrocarbolead compounds are em
lead, etc. When an aromatic cyanomanganese dicar
ployed, is from about 1:63 to about 30:1.
.
bonyl compound is added to gasoline, a substantial in
The following examples are illustrative of ?uids and
crease in the octane value of the fuel results.
fuels containing our new compounds.
The compounds can be added directly to the hydro
carbon fuels or lubricating oils and the mixture'sub 50
Example X
jected to stirring, mixing, or other means of agitation
To
1000
gallons
of
a
commercial fuel having an initial
until a homogeneous ?uid results. Alternatively, the
boiling point of 90° F. and a ?nal boiling point of
compounds of our invention may be ?rst made up into
406° F. is added 55 grams of benzene cyanomanganese
concentrated ?uids containing solvents, such as kerosene,
toluene, hexane, and the like, as well as other additives 55 dicarbonyl, and the mixture subjected to agitation until
the additive is distributed‘evenly throughout the fuel, in
such as scavengers, antioxidants and other antiknock
an amount equivalent to 0.013 gram‘ of manganese per
agents, e.g., tetraethyllead. The concentrated ?uids can
gallon of fuel.
then be added to the fuels.
Similar results are obtained with other aromatic cyano
As the organo lead antiknock agent which is an in
rnanganese dicarbonyls such as xylene cyanomanganese
gredient of certain of the compositions of this invention,
organolead compounds in general may be used. Prefer
dicarbonyl, mesitylene cyauomanganese dicarbonyl, and
able, however, are hydrocarbon lead compounds such as
the like.
tetraphenyllead, tetratolyllead, and particularly tetraalkyl
lead compounds such as tetramethyllead, tetrapropyllead
and the like. In general the amount of organolead anti
knock agent is selected so that its content in the ?nished
gasoline is equivalent to at least about 1 gram of lead
per gallon.
,
Where halohydrocarbon compounds are employed as
scavenging agents, the amounts of halogen used are given
in terms of theories of halogen. A theory of halogen is
de?ned as the amount of halogen which is necessary to
react completely with the metal present in the antiknock
mixture to convert it to the metal dihalide as, for ex
.
. Fuels containing mixtures of two or more aromatic
cyanornanganese dicarbonyls, such as the mixture of
benzene cyanomauganese dicarbonyl and xylene cyano
manganese dicarbonyl are prepared in a manner similar
to that employed in the above example.
Example X]
To 10 parts of benzene cyanomanganese dicarbonyl is
added 5 parts of ethylene dichloride and the mixture agi
tated until a homogeneous ?uid results. The manganese
to chloride atom ratio in this ?uid is 1:12 and represents
6 theories of halogen based on the manganese. This ?uid
ample, lead dihalide and manganese dihalide. In other 75 is added to hydrocarbon fuels in amounts so as to pro
3,042,693
‘from 0.01 to'0.05 percent of manganese as a compound
vide improved‘fuels containing 0.015 gram, 0.03 grain,
16 grams and 10“ grams of manganese per gallon.
of this invention is bene?cially employed as a dryer in
such
Example XII
a composition.
a
'
»
'
For example, to a typical varnish composition contain
. To 13.2 parts of ‘lead in the form of tetraethyllead ‘ of ing .100‘ parts ester gum, 173 parts, of tung oil, ‘23 parts
of linseed oil and 275 parts of white ‘petroleum naphtha
in an antiknock ?uid containing 0.5 theory of bromine
is added 3.0 parts of mesitylene cyanomanganese dicar
as ethylene dibromide and 1.0 theory of chlorine as
bonyl. The resulting varnish composition is found to
ethylene dichloride, wherein the theories of halogen are
have excellent drying characteristics. Equallygood re
based upon the amount of lead present, is added 0.015
apart of manganese in the form of mesitylene cyano-man 10 sults are obtained when other drying oil compositions
and other aromatic cyanornanganese dicarbonyl com
ganese dicarbonyl.
_
pounds of this invention are employed.
This fluid is then added to a commercial hydrocarbon
Other important usesof the aromatic cyanoman-ganese
fuel having an initial boiling point of 82° F. and a ?nal
dicarbonyl compounds of'the present invention include
boiling point of 420° F. in an amount so as to provide
13.2 ‘grams of lead and 0.015 gram of manganese per 15 the use thereof as chemical intermediates, particularly in
gallon.
.
V
'
V
'
.
the preparation of 'metal and metalloid containing poly
7
meric materials. In addition, some of the aromatic de
rivatives of this invention can be used in the manufacture
Example XIII
To a fuel containing 0.02 gram of lead per gallon as
. of medicinals and other therapeutic materials, as 'well as
7 diphenyldiethyllead, 1.0 theory of bromine as ethylene di
agricultural chemicals such as, for example, fungicides,
bromide, ‘and 0.2 theory of phosphorus in the form of tri
cresyl phosphate, is added mesitylene cyanomanganese
defoliants, growth regulants, and so on.
Having fully described the'novel compounds of the
present invention, the need therefor, and the bestjmethods
'dicarbonyl in an amount equivalent to v0.03 gram of man
ganese per gallon. This small’ amount of manganese in
devised for their preparation, We do not intend that our
the, form of the compounds of this invention provides
invention be limited except within the spirit and scope of
25
aconsiderable increase in the'antiknock quality of the
the appened claims,
'
.fuel as shown upon testing in a single-cylinder engine.
Other‘fuels and ?uids areprepared in thersame man
'her as illustrated hereinabove which contain other deposit
,rnodifying agents, such as boric acid, borate esters, boronic
‘We claim: a
1. A compound having an aromatic hydrocarbon mole
cule coordinated with manganese, the compound being
by additional coordination with two carbonyl
esters, etc. Likewise, lubricating oils containingrfrom 30 stabilized
groups and a cyano group, the aromatic hydrocarbon
about 0.1 to about 5 weight percent manganese in the
molecule contributing six electrons, thecarbonyl groups
form of the aromatic cyanomanganese dicarbonyl com
each contributing two electrons and the cyano group con
pounds of this invenion are prepared, and these lubricat
ing oils, when used in reciprocating engines, are found
to have a bene?cial effect on engine cleanliness and in
the reduction of combustion chamber deposits. ~
tributing one electron to the manganese, thereby giving
“ the manganese a total of eleven additional electrons and
resulting in the manganese atom having the electron con
7
The fuels to which the antiknock compositions of this
invention are-added may have a wide variation of com
positions. These fuels generally are petroleum ‘hydro
carbons and are usually blends of two'or more compo
?guration of krypton.
2.. The process for producing compounds having an
aromatic hydrocarbon molecule coordinated with man
40 ganese, the compound being stabilized by additional co
ordination with two carbonyl groups and a cyano group,
nents. These fuels can'contain all types of hydrocar
the aromatic hydrocarbon molecule contributing six elec
trons, the carbonyl groups each contributing two electrons
bons, including para?ins, both straight and branched
chain; ole?ns; cycloaliphatics containing para?in or. ole
?n side chains; and aromatics containing aliphaticrside
and the cyano group contributing one electron to the man
ganese, thereby giving the manganese a total of eleven
additional electrons and resulting in the manganese atom
chains. The fueltype depends on the base stock'from
which it is obtained and on the method of re?ning. For
having the’ electron con?guration of krypton, comprising
decarbonylating an aromatic hydrocarbon manganese tri
carbonyl cyanide by heating to a temperature of 20
example, it can be a straight run or processed hydrocar
bons, including thermally cracked, catalytically cracked,
reformed fractions, etc. When used for spark-?red en- '50
gines, the boiling range of the components of gasoline can
vary’ from zero to about 430‘* F.,,althoughr the boiling
300° C.
range of the fuel blend is often found to be between
an initial boiling point'of from about 80° F. to 100° F.
r and a ?nal boiling point of about 430° F. While'the
55
t
(1) the compound produced is'mesitylene'zcyanoman
i rlganese dicarbonyl; and V
(2) ,Thearomatic hydrocarbon manganese tricarbonyl
above is true for ordinary gasoline, the boiling range is
cyanide reactant is mesitylene manganese tricarbonyl
a little more-restricted in the case of aviation gasoline.
cyanide.
Speci?cations forvthe latter often call for a boiling range
of from about 82° F, to about 338° F., with certain frac
tions of the fuel boiling away atrlparticular intermediate 60
The'amount of manganese that can be employed in the
7
' temperatures.
a
3. Mesitylene cyanomanganese dicarbonyl.
4. The process of claim 2 wherein:
'
i
7
*References Cited in the ?le of this patent
UNITED STATES PATENTS
~
2,818,416
7 form of aromatic cyanomanganese dicarbonyl compounds
Brown et al _________ __‘.._ Dec. 31, 1958
of this invention in hydrocarbon fuels of the gasoline
OTHER REFERENCES
boiling range can vary from. about 0.015 to about 1.0
:grams of manganese per gallon, preferably 0.03 to v6
grams of manganese per gallon. In addition, the fuel can
also contain organolead antiknock agents such as tetra
vol. 1, pp.‘ 165-174 '(pp. 167-168 relied on).
Brook: I.A.C.S. 77, 4827-4829 (1955).
Fischer: “Chemistry and Industry,” pp. 153-154, Mar.
ethyllead in amount equivalent to from about‘ 0.02 to
3, 1956.
about 13.2 grams of lead per gallon;
, 7
_
V
_
I The aromatic cyanomanganese dicar-bonyl compounds 70
Piper et al.: .1. Inorganic and Nuclear Chem, 1955,
Fischer et al.: “Berichte” 89, 2397-2400, Oct. 3, 1956.
Nicholls et al.: “Proceedings of The Chemical Society
of this invention may be incorporated in paints, varnish,
printing inks, synthetic‘ resins of the drying oil type, oil
(London), p. 152, May 1958.
enamels and the like, to impart excellent drying char
104-124 (1956).
acteristics to such compositions.
Generally speaking,
'
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Piper et al.: “J. Inorg. Nuclear Chem.,” vol. 3, pp.
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