CA2310056A1

CA2310056A1 - Fuel compositions employing catalyst combustion structure

Info

Publication number: CA2310056A1
Application number: CA002310056A
Authority: CA
Inventors: William C. Orr
Original assignee: Individual
Current assignee: Individual
Priority date: 1998-06-17
Filing date: 1999-06-17
Publication date: 1999-12-23
Also published as: WO1999066009A3; WO1999066009A2; EP1051461A2; AU4576399A

Abstract

A fuel composition relating to a broad spectrum of pollution reducing, improved combustion performance, and enhanced stability fuel compositions for use in jet, aviation, turbine, diesel, gasoline, and other combustion applications. More particularly, the present invention relates to metallic vapor phase combustion fuel compositions employing certain co-combustion agents, including trimethoxymethylsilane.

Description

WO 99/b6009 PCTIUS99II375I
i=UEL COMPOSITIONS EMPLOYING CATALYST COMBUSTION
STRUCTURE
Field of the Invention The present invention relates to a broad spectrum of pollution reducing, improved combustion performance, and enhanced stability fuel compositions for use in jet, aviation, turbine, diesel, gasoline, and other combustion applications. More particularly, the present invention relates to fuel compositions employing certain co-combustion agents, including 1 o trimethoxymethylsilane.
Background of the Invention Growth in environmental concerns related to pollutants generated by hydrocarbon based fuels, especially emissions related to greenhouse gases, has given raise to the need to find new fuels and methods of combustion capable of reducing such emissions, namely carbon dioxide, nitrous oxide (Nx0), NOx, methane, ozone, CFC's, halons and similar gases. Increases of nitrous oxide gases occurring post exhaust catalyst have recently been discovered. Similar to CFC's, nitrous oxides are about a 1000 times more 2 o potent than C02 in their adverse effect. It has been found the effect of the exhaust catalyst, itself, may actually tend to increase the concentrations of nitrous oxides. Thus, there is a current need to reduce overall nitrous oxide emissions and additionally find a means reducing the effect the exhaust catalyst has upon increasing said emissions.
International Patent Applications, PCT/US95I02691, PCT/US95/06758, and PCT/US96109653, incorporated in their entirety herein by reference, speak to a new form of combustion known as metallic vapor combustion, wherein combustion does not take place on the surface of the metal, or on andlor within the molten layer of oxide covering the metal, typical of heretofore metallic ~mbustion. Rather, combustion is characterized by a luminous reaction zone extending some distance from the metal's surface and a high burning rate, wherein metallic oxide particles are formed in the submicron range. It is a highly expansive combustion, yielding vastly accelerated exhaust gas velocities compared to traditional combustion, in turn generating greater amounts of useable free energy.
Said PCT Applications disclose.fuel compositions and combustion techniques achieving vapor phase combustion based on an enhanced combustion structure ("ECS"), which incorporates a free radical generating oxygenate compound ("ECS oxygenate") and a high energy combustible non-lead metallic, preferably an "ECS metallic" containing ECS structure.
Applicant's metallic together with an ECS compound yield vapor phase combustion. In the aforementioned Applications and herein metallic shall mean at least one non-leaded element or derivative organic or inorganic compound containing said non-lead element, selected from the group consisting of 1A, 2A, 3B, 4B, 5B, 6B, 7B, 8, 1 B, 2B, 3A, 4A, 5A, 6A, or 7A elements of the Periodic Chart of Elements (CAS version), and mixture, wherein said element or derivative compound, is combustible, and optionally has a minimum heating 1 o value of 4,000 Kcallkg, and wherein vapor phase combustion occurs. As noted, in the aforementioned Applications and herein, an ECS metallic is a metallic capable of increasing burning velocity andlor reducing combustion temperature.
It is any non-lead metallic (or non-metallic) which may be employed in the practice of this invention. Said metallic rnay be employed with hydrogen or a hydrocarbon fuel, absent an ECS compound.
As set forth herein "ECS metallic" can be read as any non-lead metallic (and non-metallic as set forth below), or any organic or inorganic derivative thereof, which accomplishes the vapor phase combustion object of this invention. As set forth in the disclosure below ECS metallic contemplates any metallic or non-metallic accomplishing this object. An ECS metallic need not contain ECS structure (e.g. high kinetic energy free radicals), albeit said ECS
structure is preferred. A "non-lead element or derivative" herein shall also be read as "ECS metallic."
It is noted, a principal ECS metallic of the aforementioned PCT
2 5 applications was manganese, chiefly methylcyclopentadienyl manganese tricarbonyl. Due to recent concerns over the neurotoxicity of manganese combustion products, and the potential neurotoxicity of other combustion metal oxides, a need exists to find a high energy, non-manganese, non-neurotoxic replacement ECS metallic or group of metallics capable of achieving vapor 3 o phase combustion.
Example A
A fuel composition containing hydrogen or a hydrocarbon fuel and at 35 least one organic or inorganic compound containing a non-lead element, selected from the group consisting of 1A, 2A, 3B, 4B, 5B, 6B, 7B, 8, 1 B, 2B, 3A, 4A, 5A, 6A, or 7A elements of the Periodic Chart of Elements (CAS
version), wherein said non-lead derivative compound simultaneously increases combustion burning velocity andlor reduces combustion temperature, wherein said composition is improved over the hydrogen or the co-fuel alone;
optionally showing improved thermal efficiency. Said composition optionally containing an ECS oxygenate.
As noted, in the aforementioned Applications, Applicant has discovered, under these his combustion conditions, the metallic, itself, becomes an integral and powerful agent in the combustion process, improving combustion thermal efficiencies, translating into improved fuel economy, net available work, power 1 o generation, thrust, and the like (e.g. increased miles/gal.(kilometerslliter), increased flight rangelKg, increased kilowatts generatedlliter), while simultaneously reducing hazardous pollutants.
In the context of this invention, Applicant generally refers to thermal efficiency in both its chemical and mechanical context, e.g. the efficiency of the chemical reaction and the amount of useful work generated in the system, e.g.
free energy.
Applicant has found, thermal efficiency, particularly as measured as a function of net useful work generated by the system is increased. Often substantially.
2 0 For example, Applicant's has discovered thermal efficiency improvements over existing unadjusted fuels and combustion systems to be on the order of 1.0%, 2.0%, 3.0%, 4.0%, 5.0% to 20%. And, depending upon the circumstances (e.g. combustion systems, fuel configurations) average improvements can range from 2.0% to 5.0%, 5.0% to 10.0% or higher, with 2 5 modest improvements ranging from 0.05% to 1.0% to 2.0%. Exceptional improvements will range from 10%, 25% to 40%, 30% to 80%, or more.
In the context of this invention "unadjusted" fuels mean conventional existing hydrocarbon fuels concun-ent to this invention, which have not been adjusted to improve burning velocity, increase latent heats of vaporization, T-30 temperatures, mid range distillation temperatures, aromatic or sulfur contents.
These value are variously set forth herein and to the extent they are known in the industry incorporated herein by reference.
Example B
The compositions of Example A, containing hydrogen or a hydrocarbon, wherein said composition's burning velocity andlor combustion temperature permit said non-lead derivative compound to replace need for an ECS

compound, however, said composition experiencing luminous vapor phase combustion.
Example C
The aforementioned compositions, wherein said non-lead derivative is a sodium, potassium, phosphorous, boron, or silicon derivative, including mixture.
Example D
1 o The aforementioned composition, wherein said non-lead derivative is trimethoxymethylsilane or homologue, analogue, isomer or derivative.
The aforementioned PCT Applications speak to the use of symmetrical alkyl carbonates (e.g. dimethyl carbonate "DMC") as a preferred ECS
oxygenate, which the art discloses as having potential hydrolytic or stability problems when in an acidic or aqueous environments. See for example, EPO
Application # 91306278.2 Karas, which reasonably suggests fuels containing a symmetrical diakyl-carbonate, like DMC, which have pH's perhaps 11 or lower, as being potentially problematic. Thus, there is a need to mitigate this potential 2 0 fuel stability problem.
Additionally, the use of less expensive longer chain or more complex, viscous fuels, e.g., heavy oils, heavy fuel oils, diesels, etc., have attendant handling, emission and combustion problems, which warrant solution, especially if solved simultaneously with the above related problems.
Summaryr of the Invention The instant invention is an improvement to the aforementioned PCT
Applications, and simultaneously solves the noted problems. Namely, the invention reduces combustion greenhouse gases of C02, NOx, ozone, 3 o methane, and problematic chiororfluorocarbons and nitrous oxides. The invention, is particularly able to control and reduce Nx0 emissions generated post exhaust emissions catalyst.
The invention also beneficially improves a broad class of combustion systems and emissions in general, while simultaneously improving fuel economy, flight range, thrust andlor power.
The invention more particularly relates to discovery of a class of non-manganese, non-toxic ECS metal and metalloid compounds, including a combination thereof, capable of achieving vapor phase combustion, but which do not have manganese's associated neurotoxicity problem. Metallics of particular interest include alkall/alkali earth metals, sodium, potassium, boron, aluminum, silicon and phosphorus.
The invention also resides in the combination of metallics, which include combining an ECS metallic with and ECS co-combustion metal, metalloid, or carbon catalyst structurally similar to triemethoxymethylsilane or dimethyl-phosphite. Said catalyst is contemplated in combination with Applicant's ECS
metallics to improve vapor phase burning, achieving the objects of this invention.
10 The invention further resides in discovery of a means of maintaining stability of fuels containing symmetrical lower dialkyl carbonates, while simultaneously improving the handling of fuels containing alkalilalkali earth metals, which can be highly alkaline. In accordance therewith, the fuel compositions of the present invention exhibits improved stability and handling 15 attributes when the fuel compositions are constructed to a weakly alkaline (7.5 to 11.0 pH), substantially neutral (6.5 to 7.5 pH), or slightly acidic (4.5 to 6.9 pH) environments, whether or not water is present. In such cases there is no handling hazard or hydrolysis problem. Thus, in the case of symmetrical lower dialkyl carbonate containing fuels, long term storage is possible absent any 20 deterioration of stability. Likewise the handling hazards of strongly alkaline compositions due to the presence of alkaline or alkaline earth metals is additionally controlled.
Additionally, it has been discovered the presence of lower dialkyl carbonates and ECS metals in the fuel compositions of the present invention 2 5 allow for the use of highly viscous base hydrocarbon fuels, which otherwise might not be used.
Detailed Description of the Present Invention The free radical generating ECS oxygenates of this invention include C2 - C12 aldehydes (including aldehydic acids), C2 -C12 ethers (including ether acids), C3 to C15 di-ethers, C1 - C15 alcohols, C2 - C12 oxides, C3 -C15 ketones; ketonic acids, C3 - C15 esters (alkyl formates, acetates, 35 diacetates, butyrates, etc.), othroesters, C3 - C12 diesters, C5 -C12 phenols, C3 - C20 glycol ethers, C2 - C12 glycols, C3 - C20 alkyl carbonates, C3 - C20 dialkyl carbonates, C3 - C20 asymmetrical alkylldialkyl carbonates, C3 - C20 di-carbonates, C1 to C20 organic and inorganic peroxides, hydroperoxides, carboxylic acids (including formic acids), amines, nitrates, di-nitrates, oxalates, phenols, glacial acetic acids (including C3 to C8 hyrodoxy esters of acetic acid, anhydrides, methoxy methyl ester of acetic acid, etc.), boric acids, orthoborates, hydroxyacids, orthoacids, anhydrides, acetates, acetyls, nitrates, di-nitrates, vitro-ethers. Applicant's ECS compounds increasing burning velocity andlor increase latent heat of vaporization.
Applicant's ECS oxygenated compounds which include one to ten oxygen atoms are desireable, with to one to three oxygen atoms more desirable. If organic, those oxygenated compounds having carbon atoms of 10 one to 20 atoms are desireable, with one to ten more desireable, with one to five being yet more preferred. Those with three atoms or less are most preferred. Compounds where oxygen represents 10%, 20%, 30%, 40%, or more, by weight are desired. Specific oxygenated compounds can be found in detail in Or4anic Chemistry 6th Ed, T.W.G. Solomons, John Wiley & Sons, 15 N.Y., (1995), Physical Chemistry, 5th Ed, P.W. Atkins, Oxford University Press, U.K. (1994), Physical Organic Chemistry, 2 Ed, N.S. Issacs, John Wiley & Sons, N.Y. (1995) and Lan4e's Handbook of Chemistry, 14th Ed, J.A.
Dean, McGraw-Hill, N.Y. (1992).
ECS oxygenates of particular interest (homologues, analogues, 20 derivative, and isomers thereof), include tertiary hydrocarbyl ethers, including but not limited to methyl tertiary butyl ethers (MTBE), ethyl tertiary butyl ether (ETBE), tertiary methyl amyl ether (TAME), tertiary methyl ethyl ether (TEME), ethyl tertiary amyl ether; C1 to C6 aliphatic alcohois, including but not limited to ethanol, methanol; lower diakyl carbonates, including but not 25 ° limited to dimethyl carbonate (DMC), diethyl carbonate (DEC);
ethers having dual linkage (e.g. diethers), including but not limited to di-ethers, including methyal (methylene di methyl ether or dimethoxy methane), ethylal (diethoxy methane); carbons having multiple alkyloxy groups, including but not limited to tetramethoxymethane, tetraethoxymethane, anhydrides and hyrodoxy 30 esters of acetic acid, anhydrides, including but not limited to methoxy methyl ester of acetic acid, ethoxy methyl ester of acetic acid.
Applicant's ECS oxygenated compounds may be included in weight percent of the final composition in that amount, which results in optimal vapor phase combustion. Concentrations ranging from 0.5, 1.0, 1.5, 2.0, 2.1, 2.2, 35 2.5, 2.7, 3.1, 3.4, 3.5, 3.6, 3.7, 4.0, 4.5, 5.0 percent weight by oxygen are contemplated. Other oxygen concentrations range from 0.01 to 3.7, 0.1 to 80.0, 1.0 to 5.0, 1.0 to 10.0, 1.0 to 15.0, 1.0 to 20.0, 1.0 to 30.0, 1.0 to 40.0, 1.0 to 53 percent oxygen by weight in the composition.

Preferred ECS structurelcomponents (e.g. oxygenates, metallics, and hydrocarbon base, if any) are characterized as those yielding in precombustion a significant portion of reactive high kinetic energy free radicals (e.g. H, H2, O, 00, CO, F, F2, F3, N, B, Be, BO, B2, BF, AL ALO, CH3, NH3, CH, C2H2, C2H5, l_i, KO, KOO, ONH, ON, NH, NH2, OCH3, OCH, OCH2, OH, CI, CN, OCOO, COOH, C2H500C, CH3C0, OCH20, OCHCO, or CONH2), as a weight percent of their total precombustion vapors. Thus, components containing one or more of these radicals is desired. Preferred weight percent contributed by the substituent is equal to or greater than 2%, 1 o 5%, 10%, 20%, 30%, 40%, of the precombustion vapors. Similarly Applicant's ECS compounds should contain one or more radicals of same structure.
The preferred reactive high kinetic energy free radicals of this invention are those radicals that generate laminar bunsen flame velocities in excess of 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 70, 75, 80, 90 or more, cmlsec. (laminar bunsen burner flame), more preferably in excess of 50, 60, 65, or 70 cmlsec., and ideally those having at least one free or unused valency electron; said ideal radical is characterized as being a chain carrier in the main chain reaction of combustion, effectively disassociating and re-associating during combustion.
2 o As used herein flame velocity or propagation is the art definition, which can be defined as the volumetric velocity of the stream of the combustible mixture divided by the surface of the inner cone of a laminar Bunsen flame.
Thus, the preferred ECS oxygenates, metallics, andlor hydrocarbon bases, if any, have higher relative flame velocities. As a rule, when 2 5 combusted in air (as a function of their own constitution and as measured in a laminar Bunsen flame), flame velocities should equal or exceed 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 65, 70, 75, 80, 85, 90, 100, 110, 120, 130, 140, 150 cmlsec., with those exceeding 40, 41, 42, 43, 45, 47, or more, preferred.
30 The higher the burning velocity the better. It is recognized individual ECS
oxygenates may have higher burning velocities than individual metallics, compared to hydrocarbon base fuels. However, ESC oxygenatelmetallic combinations should have synergistic laminar burning velocities preferably exceeding 48, 50, 55, 60, 65, 70, or more cmlsec.
35 Preferred latent heats of vaporization of ECS components (e.g.
oxygenates, metallics, andlor hydrocarbon bases) at 60°F are those equal to or greater than 60, 75, 80, 85, 90, 95, 100, 105, 110, 115, 120, 125, 130, 135, 140, 145, 150, 155, 150, 160, 165, 170, 180, 190, 200, 210, 220, 230, 240, 250, 270, 290, 300, 325, 350, 375, 400, 425, 450, 475, 500 btul(b, or more.
Those greater than 100, 115 btu/lb are more desireable. Alternatively, preferred latent heats of vaporization (enthalpy of vaporization at boiling point) equal to or greater than 21, 22, 23, 24, 26, 27, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 40, 42, 43, 45, 47, or higher, jK mole'' are desireable, with those no less than 28.0 jK mole'', more desireable. The higher the latent heat of vaporatization the better. It is an embodiment of this invention to employ hydrocarbon bases having enhanced l_HV's (see below).
The ECS non-lead metals, metalloids, non-metals (herein "metals or 1 o metallics") are those which are combustible and which having high heating value, exceeding 2,000 to 6,000, 6,500, 7,000, 7,500, 8,000, 8,500, 9,000, 9,500, 10,000, 10,500, 11,000, 12,000, or more, Kcallkg, and which contain at least one element selected from the group consisting of aluminum, boron, bromine, bismuth, beryllium, calcium, cesium, chromium, cobalt, copper, francium, gallium, germanium, iodine, iron, indium, lithium, magnesium, manganese, molybdenum, nickel, niobium, phosphorus, potassium, palladium, rubidium, sodium, tin, zinc, praseodymium, rhenium, silicon, vanadium, strontium, barium, radium, scandium, yttrium, lanthanum, actinium, cerium, thorium, titanium, zirconium, hafnium, praseodymium, protactinium, tantalum, neodymium, uranium, tungsten, promethium, neptunium, samarium, plutonium, ruthenium, osmium, europium, americium, rhodium, iridium, gadolinium, curium, platinum, terbium, berkelium, silver, gold, dysprosium, californium, cadmium, mercury, holmium, titanium, erbium, thulium, arsenic, antimony, ytterbium, selenium, tellurium, polonium, lutetium, astatine, mixture thereof, including organic and inorganic derivatives thereof (as set forth in more detail below).
The preferred metals herein have oxides whose heats of formation are negative, and should be equal or exceed (e.g. be more negative) about -10,000 to -75,000 calorieslmole. More preferred are those equal or exceeding -100,000 to -400,000 gr calorieslmole, and greater (more negative). Simple oxides containing one or two oxygens may have heats of formation equal or exceeding -50,000 to -200,000, or greater, calories/mole are acceptabte.
VAPOR PHASE COMBUSTION
This invention contemplates a vapor phase formlmethod of combusting a metallic, wherein said method comprises: introducing kinetic free radicals having enhanced combustion structure (ECS) into a combustion chamber;

igniting and combusting a flammable metallic or metal compound in presence of said free radicals at temperature below said metal's oxide boiling point and preferably above said metal or metallic compound's boiling point; combusting said metal wherein accelerated burning occurs, as evidenced by a brilliant luminous reaction zone extending some distance from the metal's surface;
wherein metallic oxide particles resulting from combustion are in submicron range andlor remain in a gaseous state.
The composition's ingredients and proportions are tailored to accomplish this objective. Varying compositions and ingredients will 1 o necessarily yield differing results. However, in the claims below providing for vapor phase combustion, the ingredients and ranges are at a minimum optimizedlarranged to achieve this result.
NON-TOXIC ECS METALS
It is an object of this invention to eliminate neurotoxic manganese or other hazardous metal oxides of combustion, including concentrations thereof deemed to be toxic. It is a principal object of this invention to use metals and metal combinations, whose combustion products, oxides, carbonates, etc., are relatively non-toxic and absent neurotocity.
However, it is expressly recognized differing metals, and metallic blends yield different combustion products. Differing ECS metallic applications will results in different combustion products. In some applications and compositions the metal combustion products generated may be toxic. Yet in other compositions, andlor applications, the same metallic or metallics may 2 5 elicit essentially non-toxic combustion products.
Thus, it is expressly contemplated differing applications of the same metal, or differing metals acting together in combustion may produce non-toxic combustion products, while in other circumstances would produce toxic combustion products.
It is contemplated certain risk metals generating potentially toxic combustion products rnay be employed in applications where risk is acceptable, e.g. advanced jet, rocket, or outer space applications. Thus, metallics hazardous on earth could be employed in space.
It is also contemplated manganese containing metallic may be included in small concentrations in a mixture with non-manganese metallics.
For example, methylcyclopentadienyimanganese tricarbonyl may be added in small concentrations, perhaps as an anti-knock enhancer in the case of gasoline. It may be included in other fuels as well.

WO 99!66009 PCT/US99/13751 In the practice of this invention alkalilalkali earth metals, whose metal oxides are non-toxic are preferred. Particularly preferred metals include lithium, sodium, potassium, rubidium, cesium, magnesium, and calcium. More preferred are lithium, sodium, potassium and magnesium.
5 Other non-lead, non-manganese metals, whose combustion product is moderately to relatively non-toxic, and desireable in the practice of this invention, include: aluminum, boron, bismuth, cerium, gallium, lithium, potassium, sodium, phosphorus, sodium, magnesium, sulfur, chlorine, indium, iron, copper, zinc, silicon, iodine, cobalt, molybdenum, nitrogen, 10 praseodymium, rhenium, rubidium, fluorine, tin, titanium, chromium, selenium, vanadium, boron, nickel, niobium, germanium, ytterbium, yttrium, zirconium.
Blends of these metals, including their derivative compounds are contemplated.
However, slightly more desirable metals include: aluminum, boron, bismuth, calcium, cerium, cesium, gallium, lithium, potassium, sodium, magnesium, iron, copper, zinc, silicon, indium, molybdenum, nitrogen, potassium, praseodymium, rhenium, rubidium, tin, titanium, selenium, boron, germanium, ytterbium, yttrium, zirconium.
Even more desirable are aluminum, lithium, potassium, sodium, boron, 2o potassium, magnesium, silicon, nitrogen, selenium, boron, and germanium.
ft is an embodiment of this invention to substitute Applicant's non-toxic metallics for Mn in the aforementioned PCT Applications.
TESTS
2 5 As a means of illustrating the benefits of Applicant's invention, Applicant conducted a series of horse power (HP} tests employing an air cooled honda 75 cc, four stroke engine, rated at 2 horse power on a DYNOJET MODEL 100 DYNAMOMETER. Increases in HP above the engine's rate HP is an indication the vapor phase burning. Such an indication 30 would also show improvements in emissions, fuel economy, thrust, flight range, and the like, if measured. For purpose of this test only HP was measured. Certain test fuels required blending agents.
The test was conducted to show changes in rated horse power due only to changes in fuel composition. For purpose of the test the bike's 35 gasoline tank was disconnected. Tests measurements were performed after the engine had been warmed up. After each test fuel, the carburetor was drained of excess fuel and flushed to avoid fuel contamination After warm up, the test procedure included bringing the warmed bike to a stop {while engine operating), then shifting the bike into first gear and engaging the transmission and rear wheel on the dynamometer, with operator upon the bike. After shifting into second gear, the dynamometer was activated and the throttle was immediately opened to "wide open." The bike operated under full throttle until it reached a speed of about 30 mph (in second gear), when the test was terminated.
The measurement parameters included:
to A = the speed (mph) which the engine achieved its rated 2 hp.
B = the speed at which the highest rated HP was achieved.
C = the highest rated hp.
D = the speed at which horse power descended back to rated 2 hp.
E = Horse Power Factor [(D-A) x C].
F = Incremental Horse Power Factor [{D-A) x C]] minus Horse Power Factor of Base Fuel. This is an indication of additional net horse power attributed to incremental ingredients.
A B C D E F
TEST FUEL
1. Base gasoline 20 21 2.Ohp 23 6 2. Base gasoline with 2.7% 02 wt of MTBE 20 21 2.Ohp 23 6 0 (Oxygen from MTBE is 2.7% weight of composition) 3. Base gasoline with 2.5% 02 wt DMC 20 21 2.Ohp 23.5 7 1 4. Base gasoline with 3.5% 02 wt Ethanol 20 21 2.Ohp 23.5 7 1 7. Base gasoline with 18.5 21.5 2.1 hp 24.5 12.6 6.6 0.00156% vol. methoxy-methylsifane 8. Base gasoline with 18 21.5 2.1 25.0 14.7 8.7 hp 0.03125% vol trimethoxy-methylsilane 9. Base gasoline with 18 16.1 10.1 21.5 2.15hp 25.5 0.125% vol trimethoxy-l0 methylsilane 10 Base gasoline with 18 1.5 2.15hp 17.2 11.2 2 26.0 0.25% vol trimethoxy-methylsifane 11 Base gasoline with 17 21.5 2.5hp 27.0 25.0 19.0 0.03125% vol trimethoxy-methylsilane, 2.5% 02 wt DMC

2 12 Base gasoline with 16.521.5 2.60hp 27.3 21.3 0 27.0 0.03125% vo1 trimethoxy-methylsilane, 3.5% 02 wt Ethanol 13 Base gasoline with 18.521.5 2.1 hp 12.6 6.6 24.5 2 0.00156% vol dimethyl-phosphite 14 Base gasoline with 18.521.5 2.15hp 12.9 6.9 24.5 0.003125% vol dimethyl-30 phosphite 15 Base gasoline with 18.521.5 2.15hp 14.0 8.0 25.0 0.03125% vol dimethyl-phosphite 16 Base gasoline with 18.521.5 2.2hp 16.5 10.5 26.0 0.125% vol dimethyl-phosphite 17 Base gasoline with 18.5 21.5 2.3hp 26.5 18.4 12.4 0.25% vol dimethyl-phosphite 18 Base gasoline with 17.5 21.5 2.45hp 25.5 19.6 13.6 0.003125% vol dimethyl-phosphite, 2.7% 02 wt MTBE

19 Base gasoline with 17.0 21.5 2.50hp 26.5 23.8 17.8 0.03125% vol dimethyl-phosphite, 2.5% 02 wt DMC

20 Base gasoline with 19.5 21.5 2.1 hp 24.0 9.5 3.5 0.003125% wt potassium ethoxide-21 Base gasoline with 18.5 21.5 2.2hp 25.0 14.3 8.3 0.0625% wt potassium ethoxide-22 Base gasoline with 18.5 21.5 2.2hp 25.5 15.4 9.4 0.125% wt pota$sium ethoxide-23 Base gasoline with 17 21 2.5hp 27.0 25.0 19.0 0.0625% wt potassium ethoxide, 2.7 vol% MTBE
24 Base gasoline with 17.5 21 2.50hp 27.5 25.0 19.0 0.0625% wt potassium ethoxide, 2.5 vol% DMC
25 Base gasoline with 16.5 21.5 2.55hp 27.5 28.0 22.0 0.03125% wt potassium ethoxide, 2.7% 02 wt MTBE

WO 99/b6009 PCT/US99113751 26 Base gasoline with 16.5 21.5 2.60hp 27.0 27.0 21.0 0.0625% wt potassium ethoxide, 2.7% 02 wt MTBE
27 Base gasoline with 16.5 21.5 2.60hp 27.5 28.6 22.6 0.125% wt potassium ethoxide, 2.5% 02 wt DMC
28 Base gasoline with 19.5 21 2.05hp 24.5 10.2 4.2 0.003125% volume [2-{cyciohexenyl) ethyl]triethoxysilane 29 Base gasoline with 18.5 21 2.15hp 25.5 15.0 9.0 0.03125% volume [2-(cyclohexenyl) ethyl]triethoxysilane 30 Base gasoline with 18 21 2.25hp 25.5 16.9 10.9 0.125% volume [2-(cyclohexenyl) 2 o ethylJtriethoxysilane 31 Base gasoline with 16 22 2.6hp 28.0 31.2 25.2 0.0625% volume [2-(cyclohexenyl}
ethylJtriethoxysilane, 2 5 2.7% 02 wt MTBE
32 Base gasoline with 16 22 2.65hp 29.0 34.3 28.3 0.125% volume [2-(cyclohexenyl) ethyl]triethoxysilane, 30 2.5% 02 wt DMC
33 Base gasoline with 15.5 21.5 2.65hp 28.5 34.5 28.5 0.125% volume [2-(cyclohexenyl}
ethyl]triethoxysilane, 3 5 3.5% 02 wt Ethanol 34 Base gasoline with 19 21 2.05hp 25.0 12.3 6.3 0.003125% volume [2-(cyclohexenyl}
ethyl]triethoxysiiane, 0.003125 vol%
trimethoxymethylsilane 5 35 Base gasoline with 19 21 2.2 hp 25.5 14.3 8.3 0.03125% volume (2-{cyclohexenyl}
ethyl)triethoxysilane, 0.03125vo1%
trimethoxymethylsilane 10 36 Base gasoline with 19 21 2.25 hp 26.015.8 9.8 0.0625% volume [2-(cyclohexenyl) ethyl]triethoxysilane, 0.03125vo1%
trimethoxymethylsilane 15 37 Base gasoline with 19 21 2.15hp 26.0 15.0 9.0 0.003125% volume [2-(cyclohexenyl}
ethyl]triethoxysilane, 0.003125 vol%
dimethylphosphite 2 0 38 Base gasoline with 16.5 22 2.8hp 28.5 33.6 27.6 0.03125% volume [2-(cyclohexenyl) ethyl]triethoxysilane, 0.25 vol%
trimethoxymethylsilane, 2.7% 02 wt MTBE
39 Base gasoline with 17 21 2.75hp 28 30.3 24.3 0.25% volume (2-(cyclohexenyl}
ethyl]triethoxysilane, 0.25 vol%
dimethylphosphite, 2.5% 02 wt DMC
40 Base gasoline with 19 20 2.15hp 25.5 14.0 8.0 0.00625% volume hexamethyldisilane 41 Base gasoline with 18 21 2.25hp 26.5 19.1 13.1 0.0625% volume hexamethyldisilane 42 Base gasoline with 16 23 2.75hp 29 35.8 29.8 0.0625% wt potassium ethoxide, 0.03125 vol% trimethoxy methylsilane, 2.5% 02 wt DMC
43 Base gasoline with 15.5 23 2.80hp 28.5 36.4 30.4 0.0625% wt potassium ethoxide, 0.03125 vol% trimethoxy methylsilane, 3.5% 02 wt Ethanol 44 Base gasoline with 16.5 22 2.65hp 28.5 31.8 25.8 0.03125% wt potassium ethoxide, 0.0625 vol% trimethoxy methylsilane, 2.0% 02 wt MTBE
45 Base gasoline with 16.5 22 2.65hp 27.0 27.8 21.8 0.03125% wt potassium ethoxide, 0.003125vo1% dimethyl phosphate, 2.5% 02 wt DMC
46 Base gasoline with 16.0 22 2.65hp 29.5 35.8 29.8 2 0 0.003125% wt potassium ethoxide, 0.0625vo1% dimethyl phosphate, 3.5% 02 wt Ethanol 47 Base gasoline with 16 22 2.75hp 27.5 31.6 25.6 0.125% wt potassium ethoxide, 0.0625vo1% dimethyl phosphate, 2.2% 02 wt MTBE
48 Base gasoline with 16.5 21.5 2.65hp 27.5 29.2 23.2 0.03125% wt potassium phenoxide, 0.03125vo1% dimethyl phosphate, 2.2% 02 wt MTBE
49 Base gasoline with 17.0 22 2.60hp 26.5 24.7 18.7 0.03125% wt potassium tert-butoxide, 0.003125vo1% dimethyl phosphate, 1.5% 02 wt MTBE

ANALYSIS OF TEST DATA
The above data shows unexpected results and the synergistic nature of Applicant's ingredients, individually and in combination. For example, Test 3 shows gasoline with 2.5% 02 wt DMC to have an F value of 1, where F represents the incremental horse power factor due to the inclusion of DMC
(e.g. [(D-A) x C]] minus horse power Factor of Base Fuel}. Thus, the DMC fuel has a slightly higher F value than the base fuel.
1 o Test 8, gasoline with 0.03125% wt. trimethoxymethylsilane, shows an F value of 8.7, which represents an apparent increase in HP as measured by F.
Test 11 a combination of 0.03125% wt. trimethoxymethylsilane and 2.5% 02 wt DMC in gasoline has an F value of 19.0, or about 10 F numbers greater than Test 8, which shows a synergism between trimethoxymethylsilane and DMC. Similar data show similar results with dimethylphosphite.
[2-(cyclohexenyl)ethyl]triethoxysilane, hexamethyldisilane, potassium ethoxide, potassium phenoxide, dirnethylphosphite, and 2 o trimethoxymethylsilane generally show improvement alone in gasoline, but better improvement with MTBE, DMC and Ethanol, and still better improvement when either dimethylphosphite and trimethoxymethylsilane are used with the other metallics.
The HP data generally shows Ethanol, MTBE and DMC are generally 2 5 interchangeable achieving similar results. Trimethoxymethylsilane and dimethoxyphosphite also appear to be similar. It appears [2-(cyclohexenyl)ethyl]triethoxysilane, hexamethyldisilane, potassium ethoxide achieve similar results.

Example 1 A non-toxic vapor phase combustion composition comprising: 1 ) an ECS oxygenate (preferably selected from a hydrocarbyl ether, an alcohol, 35 carbonate, or methylallethylal}, 2) an ECS metallic, preferably a non-neurotoxic ECS alkalilalkali earth metallic derivative (preferably an alkyloxide of potassium or a potassium ferricyanide), or a derivative of lithium, boron, silicon, or aluminum, optionally; 3} a hydrocarbon, andlor optionally a 4) a co-combustion catalyst (preferably a silicon alkyloxy derivative, like trimethoxymethylsilane, or an alkylldialkyl phosphite like dimethyiphosphite), Examale 2 The above examples, wherein the composition constructed to have a pH ranging from 4.5 to 11.5, more preferably 5.5 to 9.5, even more preferably 6.5 to fi.9.
Example 3 The above examples, wherein the ECS metallic is an alkali/alkali earth metal (a non-limiting example, potassium ethoxide) and the co-combustion agent is a phosphorus derivative {non-limiting example dimethyl or diethyl phosphite), wherein the composition has a pH equal or less than 10.5, 9.5, 8.5, 7.5, but greater than 4.5, 5.5, or 6.0, (substantially neutral is preferred).
Example 4 The above Examples, wherein the ECS metallic is selected from alkyl metal and alkyl earth metal salts, naptha's, ferricyanides, organo-metallics (optionally containing oxygen and/or nitrogen) and derivative compound, 2o including potassium alkanols, potassium alkyl oxides, e.g. potassium methoxide, potassium ethoxide, potassium propoxide, potassium isopropoxide, potassium butoxide, potassium sec-butoxide, potassium tert-butoxide, potassium pentoxide, potassium tert-pentoxide, potassium phenoxide, etc. Other non-limiting examples of potassium salts include potassium hydrogenphthalate, potassium hydrogensulfate, monopotassium acetylenedicarboxylic acid, potassium pyrophosphate, potassium dihydrogenphosphate, potassium benzoate, potassium chloride, potassium hexoate (potassium salt hexoic acid), potassium acetates, potassium formates, potassium diphenylphosphide, potassium trimethylsilonalate, potassium phthalic acid, P-aminobenzoic acid potassium salt, monopotassium L-aspartic acid, potassium napthenate. Corresponding sodium, lithium, rubidium, cesium compounds are contemplated. Mixtures are contemplated.
Example 4A
The above examples, wherein said ECS metallic is selected from potassium ethoxide, potassium tert-butoxide, potassium phenoxide, potassium acetate, potassium napthenate and mixture.

Example 4B
The above examples, wherein said fuel contains a TMMS co-combustion catalyst.
Example 4B
The above examples, wherein said fuel contains stabilizer selected from TMMS, toluene, glycols, glycol ethers and mixture.
1 o Example 4C
The above examples, wherein the ECS component is oxygenated, selected from C2 - C12 aldehydes (including aldehydic acids), C2 -C12 ethers (including ether acids), C3 to C15 di-ethers, C1 - C15 alcohols, C2 - C12 oxides, C3 - C15 ketones, ketonic acids, C3 - C15 esters (alkyl formates, acetates, diacetates, butyrates, etc.), othroesters, C3 - C12 diesters, C5 -phenols, C3 - C20 glycol ethers, C2 - C12 glycols, C3 - C20 alkyl carbonates, C3 - C20 dialkyl carbonates, C3 - C20 asymmetrical alkyl/dialkyl carbonates, C3 - C20 di-carbonates, C1 to C20 organic and inorganic peroxides, hydro-peroxides, carboxylic acids (including formic acids), amines, nitrates, di-2 0 nitrates, oxalates, phenols, glacial acetic acids (including C3 to C8 hyrodoxy esters of acetic acid, anhydrides, methoxy methyl ester of acetic acid, etc.), boric acids, orthoborates, hydroxyacids, orthoacids, anhydrides, acetates, acetyls, nitrates, di-nitrates, nitro-ethers, homologues, analogue, derivative and mixture.
Example 5 The above Examples, wherein the ECS metallic is selected from a silicon derivative including: (2-(cyclohexenyl)ethyl]triethoxysilane, cyclohexenyl dimethoxymethylsilane, benzyltrimethylsilane, N-(3-(trimethoxysilyl)propyl)ethylene-diamine, N-1-(3-(trimethoxysilyl)-propylkliethylenetriamine, N-(3(trimethoxysilyl)propyl)-ethylenediamine; 1-(trimethyl(silyl)-pyn-olidine, triphenylsilanol, octamethyltrisiloxane, 2,2,4,4,6,6-hexamethylcyclotrisilazane, hexamethylcyctrisiloxane, hexamethyl-disilane, 1,1,1,3,3,3-hexamethyl disilazane, hexamethyldisiloxane, hexamethyldisiithiane, allyltributylsilane, tetraalkylsilanes (e.g.
tetraethylsilane, tetrabutylsilane, etc.), 3-aminopropyltriethoxy-siiane, benzytrimethylsilane, benzytriethylsilane, N-benzyltri-methylsilylamine, diphenylsilanediol, dihexylsilanediol, (trimethyl-silyl)cyclopentadiene, including homologues, analogues and derivative thereof.
Example 5A
A fuel composition containing an ECS oxygenate increasing burning 5 velocity and/or reducing combustion temperature, optionally selected from MTBE, ETBE, DMC, DEC, methylal, ethylal, methanol, ethanol, or mixture, and an ECS metal selected from methylcyciopentadienylmanganese tricarbonyl, [2-(cyclohexenyl~thyl]triethoxysilane, cyclohexenyl dimethoxymethylsilane, benzyltrimethylsiiane, N-(3-10 (trimethoxysilyl)propyl)ethylenediamine, N-1-(3-(trimethoxysilyl)propyl)diethylenetriamine, N-{3-(trimethoxysilyl)propyl)ethylenediamine, 1-(trimethyl(silyl)pyrrolidine, triphenylsilanol, octamethyltrisiloxane, 2,2,4,4,fi,6-hexamethylcyclotrisilazane, hexamethylcyctrisiloxane, hexamethyldisilane, 1,1,1,3,3,3-hexamethyl 15 disilazane, hexamethyldisiloxane, hexamethyldisilthiane, allyltributylsilane, tetraalkylsilanes (e.g. tetraethylsilane, tetrabutylsilane, etc.), 3-aminopropyitriethoxysilane, benzytrimethylsilane, benzytriethylsilane, N-benzyltrimethylsilylamine, diphenylsilanediol, dihexylsilanediol, (trimethylsilyl)cyclopentadiene, potassium methoxide, potassium ethoxide, 2 o potassium propoxide, potassium isopropoxide, potassium butoxide, potassium sec-butoxide, potassium tert-butoxide, potassium pentoxide, potassium tert-pentoxide, potassium phenoxide, potassium salt of acetic acid, potassium hydrogenphthalate, potassium hydrogensulfate, monopotassium acetylenedicarboxylic acid, potassium pyrophosphate, potassium dihydrogenphosphate, potassium benzoate, potassium chloride, potassium hexoate (potassium salt hexoic acid), potassium acetate, potassium diphenylphosphide, potassium trimethylsilonalate, potassium phthaiic acid, P-aminobenzoic acid potassium salt, monopotassium L-aspartic acid, potassium napthenate, potassium hexacyanoferrate {II), potassium hexacyanoferrate (III), potassium hexacyanocobalt II- ferrate, potassium hexacyanocobalt, potassium sodium ferricyanide, or mixture.

The above examples, wherein the ECS metallic is selected from a spiral compound based upon ferricyanhydric acid derivatives, namely ferricyanides. See Dictionary of Chemical Solubilties, supra, pages 334-342, which lists various ferrocyanides (as herein provided ferrocyanides include cyanofemates, ferricyanides, and the like), incorporated herein by reference.

Alkali and alkali earth metal ferrocyanides are desireable. Transition metal ferrocyanides are desireable. Nitrogen ferrocyanides are desireable. Non-limiting examples include: potassium hexacyanoferrate (ll) and potassium hexacyanoferrate (III) are desireable. Non-limiting examples include potassium hexacyanocobalt I I- fen-ate, potassium Hexacyanocobalt II I, potassium hexachloroosmate (IV), potassium hexachloroplatinate (IV), potassium hexafluorosilicate, potassium hexafluoromanganate (IV), potassium Hexaflourozirconate. potassium hexathiocyanatoplatinate (IV), potassium sodium ferricyanide, potassium hexacyanoplatinate, potassium to hexacyanoruthinate (//)hydrate, potassium hexacyanoplatinate (IV), potassium hexafluoroaluminate, potassium hexafluoroarsenate, potassium hexafluorophosphite, potassium hexafluorophosphite, potassium hexafluorosilicate, potassium hexahydroxyantimonate, potassium hexafluoro titante, Potassium copper ferracyanide, potassium cyanide, iron (III) ferrocyanide, sodium ferrocyanide decahydrate, magnesium ferrocyanide, magnesium potassium ferrocyanide. Naturally other cyano-spiral, including hexacyano compounds are contemplated. Substitutions for potassium and/or iron are also contemplated. Examples of such substitution include potassium hexacyanocobaltate (III}, sodium hexacyanocobaltate (III}, etc. Structurally 2o similar compounds, analogues, and homologues, etc., are incorporated herein by reference and contemplated.
Example 6a The example of 5, 5A, 6, wherein said composition contains a solvent is selected from alkyl ketones (acetone, etc.), alkyl alcohols (methanol, ethanol, isobut-anol), alkyl ethers, glycerols, alkanol amines (ethanolamine, etc.), and other solvent known in the art and soluble with said hexacyanides (herein incorporated by reference), Applicant's ECS oxygenates, and optionally with a hydrocarbon (incorporated herein by refer ence). or other known solvent is employed capable of creating a solution, which is soluble in ECS oxygenate and/or a hydrocarbon base.
Example 6b The example of 6 and 6a, containing an ECS oxygenate in a combustion improving amount, and It) a combustion improving amount of a ferricyanide; and optionally: III) a co-combustion catalyst, IV) hydrogen or a hydrocarbon base fuel, V) an oxidizer, VI) a solvent;

wherein said composition is optionally VII) characterized as having a pH of from 4.5 to 10.5; and VIII) wherein said fuel is a vapor phase composition characterized upon combustion as having a luminous reaction zone extending from surface of said element.
Example 6c The example 6, 6a and 6b, wherein the ECS oxygenate is selected from the group consisting of MTBE, ETBE, TAME, ethanol, methanol, DMC, 1 o EMC or mixture; the ferricyanide is optionally a potassium based; the composition comprises a hydrocarbon base; and the composition optionally contains a mutual solvent.
Example 7 The example of 6, wherein said hexacyanide is preferably potassium hexacyanoferrate (II) or (III), and optionally contains a mutual solvent, optionally containing a co-combustion catalyst.

The Examples above, wherein the ECS oxygenated is methyl tertiary butyl ethers (MTBE), ethyl tertiary butyl ether (ETBE), tertiary methyl amyl ether (TAME), tertiary methyl ethyl ether (TEME), ethyl tertiary amyl ether;

to C6 aliphatic alcohols, including but not limited to ethanol, methanol;
lower diakyl carbonates, including but not limited to dimethyl carbonate (DMC), diethyl carbonate (DEC); ethers having dual linkage, including but not limited to methyal (methylene di methyl ether or dimethoxy methane), ethylal (diethoxy methane); carbons having multiple alkyloxy groups, including but not limited to tetramethoxymethane, anhydrides and hyrodoxy esters of acetic acid, including but not limited to methoxy methyl ester of acetic acid, ethoxy methyl ester of acetic acid.
Example 9 A fuel composition comprising: I) an ECS oxygenate in a combustion improving amount, and II) a combustion improving amount of at least one combustible element or compound containing at least one element selected from the group consisting of aluminum, boron, bromine, bismuth, beryllium, calcium, cesium, chromium, cobalt, copper, francium, gallium, germanium, iodine, iron, indium, lithium, magnesium, manganese, molybdenum, nickel, niobium, phosphorus, potassium, palladium, rubidium, sodium, tin, zinc, praseodymium, rhenium, silicon, vanadium, strontium, barium, radium, scandium, yttrium, lanthanum, actinium, cerium, thorium, titanium, zirconium, hafnium, praseodymium, protactinium, tantalum, neodymium, uranium, tungsten, promethium, 1o neptunium, samarium, plutonium, ruthenium, osmium, europium, americium, rhodium, iridium, gadolinium, curium, platinum, terbium, berkelium, silver, gold, dysprosium, californium, cadmium, mercury, holmium, titanium, erbium, thulium, arsenic, antimony, ytterbium, selenium, tellurium, polonium, lutetium, astatine, mixture thereof, including organic and inorganic derivatives, and I I I ) a co-combustion catalyst, and IV) optionally hydrogen or a hydrocarbon base fuel, and V) optionally an oxidizer, and VI) optionally wherein said fuel composition has a pH of from 4.5 to 10.5, and VII) wherein said fuel is a vapor phase composition characterized upon combustion as having a luminous reaction zone extending from surface of said element.
Example 10 The fuel of Example 9, wherein the ECS oxygenate is selected from the group consisting of methyl tertiary butyl ethers, ethyl tertiary butyl ether, tertiary methyl amyl ether, tertiary methyl ethyl ether, ethyl tertiary amyl ether, C1 to C6 aliphatic alcohols, dimethyl carbonate, diethyl carbonate, and mixture.
CO-COMBUSTION AGENTICATALYST
As evident in the tests above, it has been found the combustion activity employing Applicant's ECS oxygenated compounds and metallics is unexpectedly improved by the combination of a co-combustion catalyst, such as trimethoxymethylsilane or dimethyl-phosphite.
As contemplated in the claims hereto, co-combustion agents may serve a multiple role, including acting as a stabilizing agents. As set forth in greater detail below TMMS and other co-catalysts acts in combination with certain beneficial components to stabilize the fuel composition. Thus, as set forth herein a co-combustion catalyst can serve as a stabilizing agent.
The co-combustion catalyst (combustion co-catalyst) is a combustible compound generally having a structure of M-r~, wherein M is a metal, metalloid, or non-metal. Selected M include, but are not limited to, carbon, silicon, germanium, tin, boron, aluminum, gallium, indium, nitrogen, phosphorus, arsenic, antinomy, bismuth, sulfur, and wherein r is either an alkyloxy, hydroxy, oxy, or carboxyl radical, and wherein n is the number up to the number of valence electrons of M or the total possible number of radicals available.
If n is greater than one, then r1, r2, etc., may be a heterogeneous or homogenous, an alkyloxy, vitro, or other radical, including an alkyl or aryl radical. If n is greater than 1, one or more r may be alkyl or cyclomatic radicals may be substituted. However, compounds with at least one alkyloxy, 2 o hydroxy, oxy, or carboxyl radical are desired. Compounds containing a blend of alkyl or alkyloxy, hydroxy, oxy, carboxyl radicals are contemplated. Thus, alkyfoxymetallics and polyalkyfoxymetallics are expressly contemplated.
If r is greater than one, then one or more r may be substituted for direct or indirectly connected ring systems, for example r1 may be a phenyl radical connected directly, or indirectly connected through an alkyl group to M, where r2, r3, etc., may be an alkyloxy or alkyl radical. Likewise, when more than one r may be substituted for sulfur, nitrogen, chlorine, fluorine, or other metal, metalloid or non-metal of this invention.
Preferred co-combustion catalysts have one or more alkyioxy, 3o carboxyl, oxy, or hydroxy radicals. More preferred catalysts have one or more alkyloxy, oxy, carboxyl, hydroxy, radicals, and at least one alkyl radical. A
ring system radical may be substituted for the alkyl radical.
Non-limiting examples of co-combustion catalyst, including derivative, analogue, homologue and isomers thereof, include polyalkyloxysilanes:

trimethoxymethyisilane, ethoxytrimethylsilane, isobutyltriethoxy-silane, tetramethylsilane, dimethoxy-methyl-vinyl-silane, methyltriethoxysilane, 3-aminopropyl-triethoxysilane, 3-aminopropyl-trimethoxysilane, vinyltrimethoxysilane, diethoxydi-methylsilane, dimethoxydimethylsilane, 5 vinyltris(2-butyldenamino-oxy)silane, tetraalkyloxysilanes (e.g.
tetramethoxysilane, tetraethoxysilane, tetrapropyloxysilane, tetraisopropylsilane, tetraisobutylsilane, etc.); alkylphosphites, polyalkylphosphites (e.g. dimethyl-phosphite, diethylphosphite, dipropylphosphite, dibutylphosphite, di-tert-butylphosphite, 1o trimethylphosphite, triethylphosphite, tripropylphosphite, triisopropylphosphite, tributylphosphite), dimethylmethylphos-phonate, diethylmethylphosphonate, P-pyrophosphate, alkylphosphoramides, polyalkylphosphoramides (e.g.
hexamethylphosphoramide, hexamethylphosphorus diamide, hexamethylphosphorus triamide, hexamethylphospophorimidic triamide, 15 triethylphosphoramide, trimethylphosphoramide, tripropylphosphoramide, triisopropylphosphoramide, tributylphosphoramide, triisobutylphosphoramide, tri-sec-butylphosphoramide, tri-tert-butylphosphoramide, triphenylphosphoramide, dimethoxyphosphorusamide (CH30)2PNH2), diethoxyphosphorusamide, dipropoxyphosphorusamide, 2 o diisopropoxyphosphorusamide, dibutoxyphosphorusamide, di-isobutoxyphosphorusamide, di-sec-butoxyphosphorusamide, di-tert-butoxyphosphorusamide, diphenoxyphosphorusamide, dimethyiphosphor-amide (CH30)2PONH2), diethylphosphoramide, dipropylphosphoramide, diisopropyfphosphoramide, dibutylphosphoramide, diisobutylphosphoramide, 2 5 di-sec-butylphosphoramide, di-tert-butylphosphoramide, diphenylphosphoramide, dimethylethylphosphoramide, diethylmethyl-phosphoramide, dipropylmethylphosphoramide, diisopropylmethyl-phosphoramide, di-butyl-methylphosphoramide, di-iso-butyfmethyl-phosphoramide, di-sec-butylmethylphosphoramide, di-tert-butyl-methyiphosphoramide, diphenylmethyl phosphoramide), trimethyl-orthoacetate, trimethylorthovalerate, trimethylorthobutyrate, trimethylorthoformate; alkyloxymethanes (tetramethoxy-methane, tetraethoxymethane, tetrapropoxymethane, tetraisopropoxy-methane, tetratertbutoxy-methane, etc.), polyalkyloxymethanes; potassium pryophosphite, trimethylorthoacetate, triethylorthoacetate, trimethylortho-butyrate, triethylortho-butyrate, trimethylorthovalerate, trimethylorthoformate, dimethoxymethane, diethoxyethane, tetramethoxymethane, tri-methoxymethylmethane, tetraethoxymethane, trimethoxymethylethane, triethoxymethylethane, trimethoxymethylmethane, triethoxy-methylmethane, glacial acetic acids, including but not limited to acetic anhydrides, (acetyloxy) acid, ethyl ester (acetyloxy) acetic acid, aminooxo acetic acid, aminooxo acetic acid hydrazide, ammonium acetate, acetoacetic acid, hydroxyacetic acid (glycolic acid), methoxyacetic acid, ethoxyacetic acid, methoxy ethyl ester of acetic acid, methoxy methyl ester of acetic acid, ethoxy methyl ester of acetic acid, ethoxy ethyl ester of acetic acid, propoxy methyl ester of acetic acid, oxoacetic acid, alkylhydroxyesters of acetic acid (including but not limited to methylesterhydro-xyacetic acid, ethylesterhydroxy-acetic acid, propylesterhydro-xyacetic acid, alkyl acetates (including methyl ester acetic acid), ethyl arsenate, ethyl arsenite, methyl ester of botanic acid, ethyl ester of botanic acid, 2-hydroxybutanic acid, 3-hydroxybutanic acid, 3-hydroxy-ethylester of botanic acid, 2-hydroxyethylester of botanic acid, diphenyl carbonate, dipropyl carbonate, ethyimethyl carbonate, dibutyl carbonate, tetranitromethane, triethylphosphine oxide, triethylphosphine oxide, triethylphosphine, diethyl-phosphinic acid, dimethylphosphinic acid, ethyl diethylphosphinic acid, diethylphosphonic chloride, dibutyl ester phosphonic acid, (1,1-dimethylethyl) phosphonic acid, ethenyl diethyl ester phosphoric acid, diethyl ethylphosphonate, ethyl dimethylester phosphonic acid, methyl 2 o dimethylester phosphonic acid, methyl monoethylester phosphonic acid, methyl monomethylester phosphonic acid, methyl-O,O-dimethylester phosphonothioic acid, diethyl ester phosphoric acid, dimethyl ester phosphoric acid, tributyl phosphate, ethylphosphate, trimethyl ester phosphoric acid, triethyl ester phosphoric acid, tripropyl phosphate, 0,0,0,-methyl ester phosphorothioic acid, diethylester phosphorous acid, dimethylester phosphorous acid, tributyi ester phosphorous acid, triphenyl ester phosphorous acid, O,O,S-tiethyl ester phosphorodithioic acid, 2-methyl-1,2,propanediol, 2-methyl-2-vitro-1,3; propanediol, 2-methyl-2-propyl-1,3,-propanediol, 1-nitrate-1,2,propanediol, 1,1',1",1'"-[methanetetrayltetrakis{oxy)]-tetrakis propane, methyl propyl ether, isopropylmethyl ether, isobutyl methyl ether, ethyl propyl ether, propylmethyl ether, butyl methyl ether, tertiary butyl methyl ether, 1,1'-[methylenebis(oxy)]bis[2-methyl-propane, 1-(1-methylethoxy)-propane, 2,2',2"-[methylidyne-tris(oxy)]tris propane, 1,1',1"-[methylidynetris(oxy)]tris[2-methyl propane, 2-methyl-1-vitro propane, 2-methyl-2-vitro propane, hyd racrylonitrile, 1,1,1-triethoxy-propane, 1,1,3-triethoxy-propane, 1,1,1-trimethoxy-propane, 1,1,3-trimethoxy-propane, 1,1,1-trifluoro-3-vitro-propane, 2-pyrrolidinone, and phenol. Similar structured compounds of aluminum, gallium, germanium, nitrogen, and sulfur are contemplated and incorporated by reference.
It is to be appreciated not every possible combination of this invention is available due to potential incompatibilities, and certain combinations are more effective than others. Thus, it is contemplated a wide range of substitution be made to best practice the invention. Where necessary mutual solvents are contemplated.
As contemplated herein and in the claims below, any reference to trimethoxymethylsilane ('TMMS") or dimethylphosphite or co-combustion catalyst contemplates substitution with one or more the above disclosed co-combustion catalysts, or any structurally similar compound. It is contemplated the majority of the Applicant's ECS metallics (including those disclosed herein), including contemplated cyclornatic metallics, alkali/alkali earth metals, metal alkanols, metallic hexacyanides, inorganic metallics and non-metals alike, which achieve vapor phase combustion on their own, can be benefited from simultaneous use of co-combustion agent. Thus, it is an embodiment of this invention, and the aforementioned PCT Applications, wherever an ECS metallic is disclosed, that a co-combustion agent be additionally added.
Example 11 A fuel composition comprising: 1 ) an ECS oxygenate, 2) a co-combustion catalyst, and optionally: 3) a hydrocarbon or 4) an ECS metallic;
said fuel optionally having a pH range of 10.5 to 4.0, 9.5 to 5.0, 8.5 to 6.0, 8.0 to 6.3, 7.8 to 6.2, 7.6 to 6.2; or optionally a pH less than 10.5, 10.0, 9.5, 9.0, 8.5, 8.0, 7.9, 7.8, 7.7., 7.6, 7.5, 7.4, 7.3, 7.2, 7.0, 6.9, 6.8, but greater than a pH of 4.0, 4.5, 5.0, 5.5, 6.0, 6.2, or 6.5, Example 11A
A fuel composition comprising: 1 ) a hydrocarbon, 2) a co-combustion catalyst, and optionally: 3) an ECS oxygenate, or 3) an ECS metallic; said fuel optionally having a pH range of 10.5 to 4.0, 9.5 to 5.0, 8.5 to 6.0, 8.0 to 6.3, 7.8 to 6.2, 7.6 to 6.2; or optionally a pH less than 10.5, 10.0, 9.5, 9.0, 8.5, 8.0, 7.9, 7.8, 7.7., 7.6, 7.5, 7.4, 7.3, 7.2, 7.0, 6.9, 6.8, but greater than a pH
of 4.0, 4.5, 5.0, 5.5, 6.0, 6.2, or 6.5, Example 11 B
A fuel composition comprising: 1 ) an ECS metallic; 2) a co-combustion catalyst, and optionally: 3) a hydrocarbon, 4) an ECS oxygenate, said fuel optionally having a pH range of 10.5 to 4.0, 9.5 to 5.0, 8.5 to 6.0, 8.0 to 6.3, 7.8 to 6.2, 7.6 to 6.2; or optionally a pH less than 10.5, 10.0, 9.5, 9.0, 8.5, 8.0, 7.9, 7.8, 7.7., 7.6, 7.5, 7.4, 7.3, 7.2, 7.0, 6.9, 6.8, but greater than a pH
of 4.0, 4.5, 5.0, 5.5, 6.0, 6.2, or 6.5, Example 12 The composition of Example 11, 11A, 11 B, wherein the a co-combustion catalyst is selected from group consisting of trimethoxymethylsilane, ethoxytrimethylsilane, isobutyltriethoxysilane, tetramethylsiiane, dimethoxy-methyl-vinyl-silane, methyltriethoxysilane, 3-aminopropyl-triethoxysilane, 3-aminopropyl-trimethoxysilane, vinyltrimethoxysilane, diethoxydimethylsilane, dimethoxydimethyfsilane, vinyltris(2-butyldenaminooxy)silane, tetramethoxysilane, tetraethoxysifane, tetrapropyloxysilane, tetraisopropylsilane, tetraisobutylsilane, dimethylphosphite, dipropylphosphite, diethylphosphite, dibutylphosphite, di-2 o tert-butylphosphite, trialkylphosphites trimethylphosphite, triethylphosphite, triisopropylphosphite, tributylphosphite), dimethylmethylphosphonate, diethylmethylphosphonate, potassium pryophosphite, trimethylorthoacetate, triethylorthoacetate, trimethylorthobutyrate, triethylorthobutyrate, trimethylorthovalerate, trimethylorthoformate, including homolgues, 2 5 analogues, isomers, derivatives, and mixture thereof.
Example 12 The fuel composition of Example 11, 11 A, 19 B, wherein the co-combustion catalyst is~ selected from group consisting of 3o trimethoxymethylsilane, dimethylphosphite, diethyphosphite, tetramethoxymethane, tetraethoxymethane, trimethoxymethylmethane, triethoxymethylmethane, methoxy methyl ester of acetic acid, tetranitromethane, and mixture.
3 5 Example 13 The fuel composition of Example 11, 11 A, 11 B, wherein the ECS
oxygenate is optionally selected from MTBE, ETBE, DMC, methanol, ethanol, methylal, or mixture, and the ECS metal is a combustible compound is selected from [2-(cyclohexenyl)ethyl]triethoxysilane, cyclohexenyl dimethoxymethylsilane, benzyltrimethylsilane, N-(3-(trimethoxysilyl)propyl)ethylenediamine, N-1-(3-(trimethoxysilyl)propyl)diethylenetriamine, N-(3-(trimethoxysilyl)propyl)ethylenediamine, 1-(trimethyl(siiyl)pyrrolidine, triphenylsilanol, octamethyltrisiloxane, 2,2,4,4,6,6-hexamethylcyclotrisilazane, 1o hexamethylcyctrisiloxane, hexamethyldisilane, 1,1,1,3,3,3-hexamethyl disilazane, hexamethyldisiloxane, hexamethyldisilthiane, allyltributylsilane, tetraalkylsilanes (e.g. tetraethylsilane, tetrabutylsilane, etc.), 3-aminopropyltriethoxysilane, benzytrimethylsilane, benzytriethylsilane, N-benzyltrimethylsilylamine, diphenylsilanediol, dihexylsilanediol, (trimethylsilyl)cyclopentadiene, potassium methoxide, potassium ethoxide, potassium propoxide, potassium isopropoxide, potassium butoxide, potassium sec-butoxide, potassium tert-butoxide, potassium pentoxide, potassium tert-pentoxide, potassium phenoxide, potassium salt of acetic acid, potassium hydrogenphthalate, potassium hydrogensulfate, monopotassium 2 o acetylenedicarboxylic acid, potassium pyrophosphate, potassium dihydrogenphosphate, potassium benzoate, potassium chloride, potassium hexoate (potassium salt hexoic acid), potassium acetate, potassium diphenylphosphide, potassium trimethylsilonalate, potassium phthalic acid, P-aminobenzoic acid potassium salt, monopotassium L-aspartic acid, potassium napthenate, potassium hexacyanoferrate (II), potassium hexacyanoferrate (III}, potassium hexacyanocobalt II- ferrate, potassium hexacyanocobalt, potassium sodium ferricyanide, or mixture.
Example 14 3 o A luminous combustion composition comprising:
I) a combustion improving amount of at least one ECS compound, said compound characterized as reducing combustion temperature and/or increasing burning velocity, having a minimum latent heat of evaporation of 21 kJ mol-' at its boiling temperature, and a minimum burning rate (as measured by laminar Bunsen flame) of 40 cmlsec, said compound optionally selected from the group consisting of alcohols, afdehydes, amines, carbonic esters, carboxylic acids, carbonates, di-carbonates, esters, di-esters, ethers, di-ethers, glycols, glycol ethers, ketones, nitrates, di-nitrates, peroxides, hydroperoxides, phenols, said compound optionally containing at least one alkyl, alkyloxy, dialkyl, dialkyloxy, polyalkyl, polyalkyioxy, aryl, amide, acetate, 5 aldehyde, carbethoxy, carbomethoxy, carbonyl, carbonyldioxy, carboxyl, ethoxalyl, ethoxy, formyl, glycolyl, glyoxylyl, hydroxyl, imide, methoxy, methyfenedioxy or nitrosyl radical, including derivatives, analogues, and homologues, and mixture;
II} a combustion improving amount of at least one non-leaded element 10 or derivative organic or inorganic compound containing said non-lead element, selected from the group consisting of 1A, 2A, 3B, 4B, 5B, 6B, 7B, 8, 1 B, 2B, 3A, 4A, 5A, 6A, or 7A elements of the Periodic Chart of Elements (CAS version), and mixture, wherein said element or derivative compound, is combustible and optionally has a minimum heating value of 4,000 Kcal/kg;
15 III) a combustion co-catalyst; optionally a:
IV} stabilizer, V) a co-fuel andlor oxidizer;
VI} wherein a luminous reaction zone extends from the surface of said non-lead element or derivative compound in combustion, optionally, where 20 resultant oxides of said non-lead element are formed in the submicron range;
and V11) wherein said composition has a thermal efficiency of at least 2%
greater than unadjusted co-fuel (if any).
25 Example 15 A fuel composition comprising:
I) a hydrocarbon fuel base; and II) an ECS oxygenate selected from the group consisting of C2 - C12 aldehydes, aldehydic acids, C2 -C12 ethers, ether acids, C1 - C15 alcohols, 30 C2 - C12 oxides, C3 - C15 ketones, ketonic acids, C3 - C15 esters, othroesters, C3 - C12 diesters, C5 -C12 phenols, C3 - C20 glycol ethers, C2 -C12 glycols, C3 - C20 alkyl carbonates, C3 - C20 dialkyl carbonates, C3 -C20 asymmetrical alkyl carbonates, C3 - C20 di-carbonates, C1 to C20 organic and inorganic peroxides, hydroperoxides, carboxylic acids, amines, nitrates, di-nitrates, oxalates, phenols, glacial acetic acids, C3 to C8 hyrodoxy esters of acetic acid, methoxy methyl ester of acetic acid,acetic acid WO 99/66009 PCT/US99/13'I51 anhydrides, methoxy methyl ester of acetic acid, boric acids, orthoborates, hydroxyacids, orthoacids, anhydrides, acetates, acetyls, formic acids, nitrates, di-nitrates, nitro-ethers; and III} an ECS metallic selected from the group consisting of [2-(cyclohexenyl)ethyljtriethoxysilane, cyclohexenyl dimethoxymethylsilane, benzyltrimethylsilane, N-(3-(trimethoxysilyl)propyl)ethyienediamine, N-1-(3-(trimethoxysilyi)propyl)diethylenetriamine, N-(3-(trimethoxysilyl)propyl)ethylenediamine, 1-{trimethyl(silyl)pyrrolidine, triphenylsilanol, octamethyltrisiioxane, 2,2,4,4,6,6-hexamethylcyclotrisilazane, 1 o hexamethylcyctrisiloxane, hexamethyldisilane, 1,1,1,3,3,3-hexamethyl disilazane, hexamethyldisiloxane, hexamethyldisilthiane, allyltributylsilane, tetraalkylsilanes {e.g. tetraethylsilane, tetrabutylsilane, etc.), 3-aminopropyltriethoxysilane, benzytrimethylsilane, benzytriethylsilane, N-benzyltrimethylsilylamine, diphenylsilanediol, dihexylsilanediol, (trimethylsilyl)cyclopentadiene, potassium methoxide, potassium ethoxide, potassium propoxide, potassium isopropoxide, potassium butoxide, potassium sec-butoxide, potassium tert-butoxide, potassium pentoxide, potassium tert-pentoxide, potassium phenoxide, potassium salt of acetic acid, potassium hydrogenphthalate, potassium hydrogensulfate, monopotassium acetylenedicarboxyiic acid, potassium pyrophosphate, potassium dihydrogenphosphate, potassium benzoate, potassium chloride, potassium hexoate (potassium salt hexoic acid), potassium acetate, potassium diphenylphosphide, potassium trimethylsilonalate, potassium phthalic acid, P-aminobenzoic acid potassium salt, monopotassium L-aspartic acid, potassium napthenate, potassium hexacyanoferrate (II), potassium hexacyanoferrate (III), potassium hexacyanocobalt II- ferrate, potassium hexacyanocobalt, potassium sodium ferricyanide, or mixture; and, IV) optionally a co-combustion catalyst; and V) optionally a hydrocarbon base; and VI) optionally an oxider, and VII) wherein said fuel is a vapor phase composition characterized upon combustion as having a luminous reaction zone extending from surface of said element.
3 5 Example 15A
The above examples, wherein said fuel optionally contains a viscous hydrocarbon base andlor an oxidizer. Said fuel further characterized as having a pH of 10.5 or less. When this fuel composition contains a hydrocarbon base, said base may have a viscosity outside normal industry standards (as set forth above). However, resultant fuel's viscosity is within industry standards.
Example 16 The example compositions above, wherein the oxygenate is selected from MTBE, ETBE, TAME, methanol, ethanol, DMC, DEC, or mixture, and 1 o said ESC metal is optionally hexamethyldisilane.
Example 17 The example compositions above, wherein the oxygenate is selected from MTBE, ETBE, TAME, methanol, ethanol, DMC, DEC, or mixture, and said ECS metallic is optionally potassium ethoxide.
Example 18 The fuel compositions above, wherein the oxygenate is selected from MTBE, ETBE, TAME, methanol, ethanol, DMC, DEC, or mixture, and said 2o ECS metallic is optionally [2-(cyclohexenyl)ethyl)triethoxysilane.
Example 19 The fuel compositions above, wherein the oxygenate is selected from MTBE, ETBE, TAME, methanol, ethanol, DMC, DEC, or mixture, and said ECS metallic is optionally potassium hexacyanoferrate (II), potassium hexacyanoferrate (I I I ), potassium hexacyanocobalt II- ferrate, potassium hexacyanocobalt, potassium sodium ferricyanide, or mixture.
Examplg 20 3o The above compositions, wherein the oxygenate is a dialkyl carbonate and the pH is substantially neutral.
Example 21 A fuel composition comprising:
I) a hydrocarbon fuel base, and II) a co-combustion agent selected from the group consisting of trimethoxymethylsilane, ethoxytrimethylsilane, isobutyltriethoxysilane, tetramethylsilane, dimethoxy-methyl-vinyl-silane, methyltriethoxysilane, 3-aminopropyl-triethoxysilane, 3-aminopropyl-trimethoxysilane, vinyltrimethoxysilane, diethoxydimethylsilane, dimethoxydimethylsilane, vinyltris(2-butyldenaminooxy)silane, tetramethoxysilane, tetraethoxysilane, tetrapropyloxysilane, tetraisopropylsilane, tetraisobutylsilane, dimethylphosphite, dipropylphosphite, diethylphosphite, dibutylphosphite, di-tert-butylphosphite, trialkylphosphites trimethylphosphite, triethylphosphite, triisopropylphosphite, tributylphosphite), dirnethylmethylphosphonate, diethylmethylphosphonate, potassium pryophosphite, trimethylorthoacetate, triethylorthoacetate, trimethylorthobutyrate, triethylorthobutyrate, trimethylorthovalerate, trimethylorthoformate, including homolgues, analogues, isomers, derivatives, and mixture thereof.
Example 22 A fuel composition comprising: a hydrocarbon base; a combustion improving amount of an ECS metal is a combustible compound is selected from methylcyclopentadienylmanganese tricarbonyl, [2-(cyclohexenyl)ethyl]tri-ethoxysilane, cyclohexenyl dimethoxymethylsilane, benzyltrimethylsilane, N-(3-{trimethoxysilyl)propyl)ethylenediamine, N-1-(3-(trimethoxysilyl)propyl}diethylenetriamine, N-(3-(trimethoxysilyl)propyl)ethylenediamine, 1-{trimethyi(silyl)pyrrolidine, triphenylsilanol; octamethyltrisiloxane, 2,2,4,4,6,6-hexamethylcyclotrisilazane, 2 5 hexamethylcyctrisiloxane, hexamethyldisilane, 1,1,1,3,3,3-hexamethyl disilazane, hexamethyldisiloxane, hexamethyldisilthiane, allyltributylsilane, tetraalkylsilanes (e.g. tetraethylsilane, tetrabutylsilane, etc.), 3-aminopropyltriethoxysilane, benzytrimethylsilane, benzytriethylsilane, N-benzyltrimethylsilylamine, diphenylsilanediol, dihexylsilanediol, 3o (trimethylsilyl)cyclopentadiene, potassium methoxide, potassium ethoxide, potassium propoxide, potassium isopropoxide, potassium butoxide, potassium sec-butoxide, potassium tart-butoxide, potassium pentoxide, potassium tart-pentoxide, potassium phenoxide, potassium salt of acetic acid, potassium hydrogenphthalate, potassium hydrogensulfate, monopotassium 35 acetylenedicarboxylic acid, potassium pyrophosphate, potassium dihydrogenphosphate, potassium benzoate, potassium chloride, potassium hexoate (potassium salt hexoic acid), potassium acetate, potassium diphenylphosphide, potassium trimethylsilonalate, potassium phthalic acid, P-aminobenzoic acid potassium salt, monopotassium L-aspartic acid, potassium napthenate, potassium hexacyanoferrate (II), potassium hexacyanoferrate (III), potassium hexacyanocobalt II- ferrate, potassium hexacyanocobalt, potassium sodium ferricyanide, or mixture; optionally a combustion improving amount of an ECS oxygenate selected from MTBE, ETBE, DMC, methanol, ethanol, or mixture; optionally a co-combustion catalyst.
Example 23 The composition of 21, wherein the ECS metallic is selected from 1 o potassium ethoxide, [2-(cyclohexenyl}ethylJtriethoxysilane, potassium hexacyanoferrate (II), potassium hexacyanoferrate (III}, potassium hexacyanocobalt I I- ferrate, potassium hexacyanocobalt, potassium sodium ferricyanide, or mixture.
Example 24 The composition of 21, wherein an ESC oxygenate is employed.
Example 25 The composition of 21, containing a co-combustion agent iselected 2 0 from the group consisting of trimethoxymethylsilane, ethoxytrimethylsilane, isobutyltriethoxysilane, tetramethylsilane, dimethoxy-methyl-vinyl-silane, methyltriethoxysilane, 3-aminopropyl-triethoxysilane, 3-aminopropyl-trimethoxysilane, vinyltrimethoxysilane, diethoxydimethylsilane, dimethoxydimethylsilane, vinyltris(2-butyldenaminooxy)silane, 2 5 tetramethoxysilane, tetraethoxysilane, tetrapropyioxysilane, tetraisopropylsilane, tetraisobutylsilane, dimethylphosphite, dipropyiphosphite, diethylphosphite, dibutylphosphite, di-tert-butylphosphite, trialkylphosphites trimethylphosphite, triethylphosphite, triisopropylphosphite, tributylphosphite), dimethyimethylphosphonate, diethylmethylphosphonate, potassium 3 o pryophosphite, trimethylorthoacetate, triethylorthoacetate, trimethytorthobutyrate, triethylorthobutyrate, trimethylorthovaferate, trimethylorthoformate, including homolgues, analogues, isomers, derivatives, and mixture thereof.
35 Example 26 The example of various fuel compositions contained herein, containing a hydrocarbon base, whose viscosity is greater than acceptable industry standards (as set forth above); wherein the resultant fuel composition has a pH of less than 11 (more preferrable less than 10.5, 10.0, 9.5, 9.0, 8.5, 8.0, 7.5, 7.0, 6.9, 6.8, but a above 4.5, 5.5, fi.0, 6.3, 6.5 or the other ranges set forth herein, and wherein the resultant fuel meets acceptable industry standards for viscosity.

Example 27 An improved fuel composition containing an alkyl carbonate (dimethyl andlor diethyl carbonate) an ECS metal selected from an alkali/alkali earth 1o metal derivative, and optionally a co-combustion catalyst, a hydrocarbon base or co-fuel(propellant}, andlor oxidizer, wherein the pH is less than about 10.5, 9.0, 8.0, 7.5, 7.0, 6.9, or less, but greater than 4.5, 5.5, or 6.3.
STABILIZERS
In the practice of this invention, certain metallic (non-metallic) formulations are hydroscopic or tend to destabilize particularly when in combination with hydrocarbon co-fuels. For example, Applicant has found alkali/alkali earth metals to be particularly susceptible to destabilization, especially where there is a presence of water. Other formulations need to be stabilized due to the presence of Applicant's ingredients. Fuel destabilization can be undetectable, to mild, to severe, and ultimately result in the complete fuel oxidation.
Thus, it is an embodiment to employ certain classes of stabilizers.
Several are also act as co-combustion agents andlor ECS compounds.
Principal stabilizers include ployalkyloxysilanes, glycols, glycol ethers, including alkylene glycols, glycol esters, glycol acetates, and aromatic hydrocarbons, aromatic solvents, including toluenes, naphthalenes, napthas and the like.
Non-limiting examples of contemplated polyalkyioxysilanes include trimethoxymethylsilane, and those compounds, including homologue, analogue, isomers, and derivative, which are set forth above in co-combustion catalyst. Applicant has found TMMS is be particularly useful.
Non-limiting examples of glycols and glycol ethers contemplated include C3 to C15 alkylene glycol monolpoly alkylethers, including ethylene glycol monoalkyl ethers, diethylene glycol monoalkyl ethers, ethylene glycol polyalkyl ethers, diethylene glycol poiyalkyl ethers. Other non-limiting examples of glycols and related compounds include alkyioxy polyethylene glycols, alkyloxypolyglycols, alkyloxypolyglycol ethers, alkylene glycol acetates, alkylene glycolslesters/etherslacetatesl diacetateslamineslglycerols/formateslcarbinols/carbitolsl nitrites, and the like, and polyalkylene glycolslesters/ethersl acetatesldiacetateslamineslglycerols/formates/carbinolslcarbitolslnitriles, and the like.
Non-limiting examples include: diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol diisopropyl ether, diethylene glycol dibutyl ether, diethyiene glycol 1o dipentyl ether, diethylene glycol dihexyl ether, diethyiene glycol monomethyl ether, diethylene glycol monoethyl ether, diethyiene glycol monopropyl ether, diethylene glycol monoisopropyl ether, diethylene glycol rnonobutyl ether, diethylene glycol monopentyl ether, diethylene glycol monohexyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, ethylene glycol diisopropyl ether, ethylene glycol dibutyl ether, ethylene glycol dipentyl ether, ethylene glycol dihexyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monopentyl ether, ethylene glycol 2,o monohexyl ether, methoxy diethylene glycol, ethoxy diethylene glycol, propoxy diethylene glycol, butoxy diethylene glycol, methoxy ethylene glycol, ethoxy ethylene glycol, propoxy ethylene glycol, butoxy ethylene glycol, methoxyglycol, ethoxyglycol, propoxyglycol, butoxyglycol, pentoxyglycol, methoxydiglycol, ethoxydiglycol, propoxydiglycol, butoxydiglycol, 2 5 pentoxydiglycol, methoxytriglycol, ethoxytriglycol, propoxytriglycol, butoxytriglycol, pentoxytriglycol, methoxytertglycol, ethoxytertglycol, propoxytertglycol, butoxytertgiycol, pentoxytertglycol. Also contemplated are Union Carbide's Cellosolve solvents, including Methyl Cellosoive, Ethyl Cellosolve, Propyl Cellosolve, Butyl Cellosolve, Pentyl Cellosolve, Hexyl 3o Cellosolve; Union Carbine's Carbitol solvents, including Methyl Carbitol, Ethyl Carbitol, Propyl Carbitol, Butyl Carbitol, Pentyl Carbitol, diethyl carbitol and the like.
Additional non-limiting examples of other acceptable glycols include:
triethylene glycol, 3-aminopropyl ether triethylene glycol, diacetate triethylene 35 glycol, monobutyl ether triethylene glycol, monomethyl ether triethylene glycol, monopropyl ether triethylene glycol, tetraethylene glycol, dibutoxytetraethylene glycol, diacetate tetraethylene glycol, aminopropyl ether tetraethylene glycols, monobutyl ether tetraethylene glycol, monomethyl ether WO 99!66009 PCT/US99l13751 tetraethylene glycol, dimethyl ether tetraethylene glycol, diethyl ether tetraethylene glycol, monoethyl ether tetraethylene glycol, monopropyl ether tetraethylene glycol, tetraethylenepentamine, tripropylene glycol, tetrapropylene glycol, dipropylene glycol, propylene glycol monornethyl ether, propylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol, ethylene glycol, hexylene glycol, dipropylene glycol, diethylene glycol, triproylene glycol, tetraethyiene glycol, tetramethylene glycol, tetrapropylene glycol, polyethylene glycol (200, 300, 400, 600, 1000, 1500, 1540, 4000, 6000 Ashland Chemical), polyethylene glycol 3350 (Spectrum), polypropylene glycol (P400, P1200, P2000, P4000 Ashland Chemical), diacetate diethylene glycol, diethyl ether diethylene glycol, dioleate diethylene glycol, mono (2 hydroxylpropyl) ether diethylene glycol, monomethyl ether acetate diethylene glycol. In the practice of this invention, homologues, analogues, isomers and derivative of the above stabilizers are contemplated.
Other non-limiting stabilizers include nonvolatile, nonion compounds, including alkylanoic acids (ethanoic, propanoic, butanoic, pentanoic, and 2 o hexanoic acids), their acetates, esters and ethers. Related ethenes, butenes, propenes, hexenes, pentenes are acceptable.
Other stabilizers of this invention may be selected from alcohols, ketones, ethers, esters, phenols, acetals, acid azides, acid halides, acids and acid derivatives (aldehydic, aliphatic dicaroxylic, alipatic monocarboxylic, aliphatic polycarboxylic, amino acids, hydroamic, hydroxyacids, imidic, ketonic, nitrolic, orthoacids, peracid, etc.), acetic acids, acetic anhydrides, acetic acid esters, aldehydes, aliphatic hydrocarbons (including high boiling point material), amides, amidines, amidoximes, anhydrides, aromatic hydrocarbons, azides, azines, azelates, azo compounds, betaines, bromoactealdehydes, bromoethanes, bromoethylenes, bromoacetic acids, bromobutanes, bromobutenes, bromobutylenes, bromo ethers, di bromo compounds, butyric acids, butanoic acids, butanoic esters, esters, orthoesters, acetates, ethylene acetates, esters, hydrates, hydrides, hydroperoxides, hydroxamic acids, hydroxyacids, imides, imidic acids, imines, ketenes, lactams, lactones, glycolic acids, butyric acids, heptic acids, valeric acids, isocaproic acids, nitrolic acids, nitrosolic acids, octanoic acids, esters of octanoic acids, opium compounds, orthoacids, ortho borates, octynes, octenes, octanones, oximes, esters of oxalic acid, oxalic acids, ethanoic acids, esters of ethanoic acids, esters of nonanoic acids, propanoic acids, esters of propanoic acid, pentanoic acids, propanediones, propanones, ethenes, propenes, butenes, pentanes, petenes, hexenes, esters of pentanoic acids, butanoic acids, oxalic esters, esters of butanoic acids, pentaneoic acids, esters of pentaneoic acids, pentanedioic acids, esters of pentanedioic acids, 2- or 3-pentanones, hexanoic acids, esters of hexnoic acids, heptanoic acids, esters of heptanoic acids, esters of formic acid, glycol 1o esters, octenes, octanone(s), oxalic acids, esters of oxalic acids, esters of hexanoic acid, hexanones, pentanedials, peroxides, furans, esters of 2-furancarboxylic acids, furfurals, propenes, propenoic acids, esters of propenoic acids, ethers, butenedioc acids, bromo-alcohols, ethanetriols, propanetriols, butanetriols, pentanetriols, naphthalenes, hexanetriols, septanetriols, octanetriols, nitrobenzene, iodobenzene, 2-nitrophenol, cyclohexylamine, dibutylamine, diethylamine, diethylenetriamine, diethylethanolamine, diisopropanolamine, morpholine, triethylamine, triethylenetetramine, triisopropanolamine, amino methyl propanol, propylene oxide, propylene glycol, 1,2 propanediol carbonate, salicylic acid, succinic 2 o acid, tartaric acid, tannic acid, 2,2,4-trimethylpentane, dimethylbenezenes, dimethyl formamide, n-methyl-2 pyrrolidone, amyl alcohol (primary), cyclohexanol, 2-ethylhexanol, methyl amyl alcohol, tetrahydrofurfuryl alcohol, TEXANOL ester alcohol (Eastman Chemical), UCAR Filmer IBT (Union Carbide Corp.), amyl acetate, dibase ester, ester solvent EEP (Ashland Chemical), 2-ethylexyi acetate, glycol ether acetates (DB, DE, DPM, EB, EE, PM, Ashland Chemical), isobutyl acetate, isobutyl isobutyrate, n-pentyl propionate, cyclohexanone, 2-hexanone, 3-hexanone, 2-methyl-3-pentanone, 3-methyl-2-pentanone, 4-methyl-2-pentanone, 3,3-dimethyl-2-butanone, diactone alcohol, diisobutyl ketone, ethyl methyl ketone, pinacolone, 3o methone, 3,3-Biphenyl 2-butanone, 1-hydroxy 2-butanone, 3-hydroxy-(dl) 2-butanone, 3-methyl 2-butanone, oxime 2-butanone, 2-butanone, 2-methyl proponoic acid, cyclopentanone, cyclopropyl methyl ketone, 2-tetrahdrofurylmethanol, cyclohexanone, isophorone, methyl amyl ketone, methyl isoamyl ketone, acetonylacetone, acetic anhydride, benzyl alcohol (a-hydroxytoluene) and variations, triisobutylene, tetraisobutylene, allylidene diacetate, acetol, 1 (4-methyoxyphenyl~2- propanone, isobutyrophenone, acetonylbenzene, butyl acetate, aliphatic alcohols, n-butyibutyrate, cetyl alcohol, cyclohexane, cyclohexanol, cyclohexanone, diethylphthalate, 2,5 WO 99/b6009 PCTNS99/13751 dimethoxytetrahydofuran, p-dioxane, 1,3-dioxane, 1,4-dioxane, 5-hydroxy-2-methyl-1,3-dioxane, glycol methylene ether, propylene carbonate, isopropylene carbonate, glycerin, 1,2,3-propanetriol, heptane, n-hexane, 2-methylpentane, 3-methylpentane, methycyclopentane, 1,4-benzenediol, isopentyl alcohol, methyl ethyl ketone, 4-methyl-2-pentanone, methyl propyl ketone, diisopropyl ketone, 1- or 3- or 4- or 5 hydroxy 2- pentanone, diisopropyl ketone, methyl propyl ketone, diacetone alcohol, isopentyl phenyl ketone, 2-pentanone, diacetone alcohol, isopentyl phenol ketone, n-butyl phenol ketone, i-butyl phenol ketone, 2-butyl phenol ketone, isopropyl acetone, 2- or 3- or 4-methoxy phenol, dehydrate oxalic acid, pentane, phenol, 3-methoxy phenol, 1,2 or 1,3 or 1,4 or 2,4 or 2,5 or 2,6 or 3,4 or 3,5 dimethyphenol, 1-octene, isobutyl 2-methylpropanate, 2-phenoxyethanol, ethylene acetate, ethyl acetate, acetonphenone, benzyl acetate, 1,3 or 1,4 or 2,3 butanediol, formaldehyde, formamide, triethyl ester orthoacetic acid, trimethyl ester orthoacetic acid, oxalic ester (diethyl ester oxalic acid), methyl hydroperoxide, ethyl hydroperoxide, acetyl peroxide, ethyl peroxide, di(tert-butyl) peroxide, acetic anhydride, 2-ethyl butyl ester acetic acid, cresyl acetates, methylglycolate, methylester phenoxy acetic acid, nitrite acid, butyric acid, butanoic acid, 2-butyl butanoic acid, 2-ethyl butanoic acid, tert-2o butyl butanoic acid, butyl nitril, propyl ester butanic acid, diethyl acetic acid, acetonacetic acid, allyl acetoneacetate, diacetylacetone, acetylacetone, ethyl ester benzoic acid, butanic methyl ester, butanic ethyl ester, butanic propyl ester, isoamyl butyrate, propyl ester butanoic acid, hexyl ester butanoic acid, 2-methyl-{d) butanoic acid, 2-methyl-{dl) butanoic acid, ethyl ester 3-methyl butanoic acid, methyl ester 3-methyl butanoic acid, isopropyl ester 3-methyl butanoic acid, 2, 2-dimethyl butanoic acid, allyl ester butanoic acid, amide butanoic acid, N,N-dimethyl butanoic acid, anhydride butanoic acid, butyl ester butanoic acid, pentyl ester butanoic ester, propyl ester butanoic acid, diethylacetic acid, 2-methyl-(d) butanic acid, methyl acetoacetate, ethyl 3o acetoacetate, diethyl acetal, acetate, acetyl acetone, 2,2-dimethyl ether ester propanoic acid, 2-oxo ethyl ester propanoic acid, 2-oxo methyl ester propanoic acid, 2-oxo isobutyt propanoic acid, 2-oxo-isopropyl propanoic acid, methyl ester propanoic acid, ethyl ester propanoic acid, propyl ester propanoic acid, propanoic acid, giyceric acid, 1, 2 dimethoxethane, 1,2 3 5 ethanediol, 1,3 butanediol, 2,3 butanedione, 1,2,3 butanetriol, 1,2,4 butanetriol, glutaric acid, glutaric anhydride, glutaronitrile, 1,5 pentanedial, glutaraldehyde, 2,4 pentadione (CH3COCH2COCH3), pentanic acid, levulinic acid, {CH3COCH3COC02H), dimethyl suberate, octanedioc acid, i,2,3 pentanetriol, 2,3,4 pentanetriol, formamide, bromoacetic acid, acetamide, pyruvic acid, methyloxyacetic acid, propionamide, allyl bromide, diethyl acetal propenal, diacetate propenal, propenal, 1,2 propanediol, 1,3 propanediol, glycerol, trimethyl ether glycerol, acetylpropionyl, acetylacetone, propionic 5 acid, methyloxyacetic acid, propionamide, malefic anhydride, eis-crotonic acid, dimethyl oxalate, isobutyric acid, hydroxyisobutyric acid, ethanetriols, propanetriols, butanetciols, pentanetriols, hexanetriols, septanetriols, 1,2,3 butanetriol, 2,3,4 pentanetriol, 1,2,3 pentanetriol, 1,2,3 propanetriol, dioxypentane, 2,4-dioxypentane, hexantriols, monobutyl ether triethylene l0 glycol, propanoic acid, anhydride propanoic acid, butyl ester propanoic acid, ethyl ester propanoic acid, pentyl ester propanoic acid, octyl ester propanoic ester, pimelic acid, suberic acid, azelaic acid, methacrylic acid, dibromobutanes (e.g. 1,2; dl-2,3; 1,4; meso-2,3; etc), tribromobutanes (e.g.
1,1,2; 1,2,2; 2,2,3; etc.), diacetamide, di(2-bromoethy!) ether, 2-ethylhexanol, 15 furfuryl alcohol, 2-propanone, 2-propen-1-ol, ethyl methanate, methyl ethanate, pentadioic acid, pentadioic acid diethyl ester, pentadioic acid dimethyl ester, pentadioic acid dinitril, 2,3-pentaedione, 2,4-pentadione, 1,2,3-pentanetriol, pentanoic acid, pentanoic acid methyl ester, pentanoic acid butyl ester, pentanoic acid ethyl ester, pentanoic acid furfuryl ester, pentanoic acid 2 o hexyl ester, pentanoic acid nitrite, pentanoic acid octyi ester, pentanoic acid pentyl ester. Also included are alkyllpolyalkyl/alkylene/ polyalkylene carbinols (non-limiting examples include, carbinol, methyl carbinol, ethyl carbinol, propyl carbinol, methyl ethyl carbinol, butyl carbinol, diethyl carbinol, methyl n-propyl carbinol, dimethyl isobutyl carbinol, ethyl isopropyl carbinol, ethyl isopropyl 2 5 methyl carbinol, diisopropyl carbinol, triethyl carbinol, isoamyl carbinol, dimethyl n-propyl carbinol, 2-butyl methyl carbinol, methyl isobutyl carbinol, diethyl methyl carbinol), methyl propyl ketone, methyoxacetic acid, acetoacetic acid, methyl acetate, tert-amyl acetate, ethyl acetate, glycol diacetate, 1,2-propendiol carbonate, 1,2-propanediol, 1,3-propanediol, 30 adiponitrile, 2-amino-2-methyl-1-propanol, triethyienetetrarnine, butyl acetate, dimethylaniline, di-n-propylaniline, methyl isobutyl ketone, n-amyl cyanide, di-n-butyl carbonate, diethylacetic acid, diethyl formamide, diisobutyl ketone, ethyl benzoate, ethyl phenylacetate, heptadecanol, 3-heptanol, n-heptyl acetate, n-hexy ether, methyl isopropyl ketone, 4-methyl-n-valeric acid, o-35 phenetidine, tetradecanol, triethylenetetramine, 2,fi,8-trimethyl 4-nonanone, ethanedial, carbonate 1,2-ethanediol, diacetate 1,2-ethanediol, dimethyl ether 1,2-ethanediol, dinitrate 1,2-ethanediol, n,n-di-methyl formic acid, n,n-di-ethyl formic acid, butyl ester formic acid, isoamyl formate, octyl ester formic acid, WO 99166009 PCT/US99l13751 pentyl ester formic acid, propyl ester formic acid, isobutyl ester formic acid, propargl acetate, 2-methoxyethanol, cyclopentanone, cyclopropyl methyl ketone, ethyl propenoate, 3-methyl-2-butanone, phenol, 2-or 3-or 4-methoxyphenol, propanoic anhydride, cyclohexanone, 4-methyl-3-penen-2-one, 2- or3- Hexanone, [2, 3 or 4]-methyl-[2 or3]-pentanone, 2-heptanone, methyl phenyl ketone, diethyl benzene, and azulene.
Fuel soluble aromatic hydrocarbons are acceptable stabilizers.
Benzene ring compounds and derivative are contemplated (including toluene, phenyl and derivative). Toluene is a preferred. Non-limiting examples of 1 o aromatic hydrocarbon stabilizers include benzene, toluene, benzaldehyde, benzin, benzl alcohol, toluene bromides, toluene cresols, toluene dimethyl amino compounds, toluene ethers, toluene oxyls, toluene alcohols. For other example, see the benzene ring compounds and derivative in CRC Handbook in Chemistry and Physics. 75th Ed, Lide, CRC Press (1994-1995), "Phyical Constants of Organic Compounds," Oroanic Chemistry 6th Ed, T.W.G.
Solomons, John Wiley & Sons, N.Y., (1995), Physical Chemistry, 5th Ed, P.W. Atkins, Oxford University Press, U.K. (1994), Ph sly cal Organic Chemistry, 2 Ed, N.S. Issacs, John Wiley & Sons, N.Y. (1995) and Lan e's Handbook of Chemistry, 14th Ed, J.A. Dean, McGraw-Hill, N.Y. (1992}, are hereby incorporated herein by reference.
Examples 27A
The above compositions containing an ECS metallic selected from 2 5 group of alkali or alkali earth metals, including derivative compounds, said composition additionally containing a stabilizer selected from the group of trimethoxysilane, toluene, a glycol, a glycol ether (including mono/polyalkylene glycol monolpolyalkylethers), including homologue, analogue and derivative compounds and mixture.
pH MODIFICATION
A desirable pH range of the fuel composition of the present invention, 3 5 particularly when DMC is employed, is from approximately 4.5 to approximately 10.5, with a more desirable pH range of from approximately 4.5 to approximately 9.5. An even more desireable pH range is from WO 99/66009 PCTlUS99113751 approximately 4.5 to 9Ø Another highly preferred pH range is from approximately 5.5. to 8Ø A preferred pH range is from approximately 4.5 to approximately 6.5. The most preferred pH range for the fuel composition of the present invention is from approximately 6.3 to approximately 6.8. It is an object of this invention to keep pH as close to neutral as possible, such that if alkaline, it is only weakly alkaline (i.e., preferably equal or less than 11.0, 10.5, 10.0, 9.5, 9.0, 8.5, 8.0 pH), but that it preferably be either substantially neutral (i.e., 6.5 to 7.5) or slightly acidic (6.3 to 6.9 pH).
When the pH of the fuel composition of the present invention is less l0 than 11.0, preferably 10.5 or below, 9.5 or below, and more preferably 8.5 or below, the fuel, whether anhydrous or hydrous, may be stored at ambient temperature (65°F) and as high as 95°F for up to 6 months, or more, absent hydrolysis.
For example, Applicant tested a fuel containing 5% by volume dimethyl carbonate, 95% by volume unleaded regular grade commercially available 87 octane (R+M)12, 118 gram Mnlgal of methylcyclopentadienyl manganese tricarbonyl, a pH of 7.0, and 5% by volume of water, which was stored for six months at temperature ranging from 65°F to 90°F. Afterwards, the fuel exhibited no hydrolysis.
2 o The same fuel composition was subsequently titrated with glacial acetic acid to a pH of 6.4, still containing 5% by volume of water and was then stored for sax months under the same conditions. After which period the fuel exhibited no signs of hydrolysis.
However, the same fuel composition was prepared with a pH of approximately 11.0, and contained 5% by volume of water and was stored for six months under the same conditions. The fuel showed slight evidence of hydrolysis. The same fuel with an adjusted a pH of 12.5, however, showed even stronger evidence of hydrolysis.
It should be appreciated that although acetic acid was used to acidify the pH of the fuel in the present test case, other fuel soluble acids, including but not limited to benzoic acid derivatives e.g. 2,4-dimethyl benzoic acid, methyl red, p-tert-butylbenzoic acid, 2-(1-methylethyl) benzoic acid, benzoic acid anhydride, 4-benzoyl benzoic acid, 2,4-dihdroxy benzoic acid, 2,4-dimethyl-benzoic acid, 3-ethoxy benzoic acid, 2-hydroxy-4-methyl benzoic acid, 2-hydroxy benzontrile, 4-methoxy benzotrile, acetic acid derivatives, e.g.
anhydride acetic acid, chloroacetic acid, decyl ester acetic acid, dibromoacetic acid, and the like, may be employed. Fuel soluble acids are incorporated by reference. See for example CRC Handbook of Chemistry and Physics. 75th Ed, Lide, CRC Press (1994-1995) "Dissociation Constants for Inorganic Acids and Bases," and "Dissociation Constants for Organic Acids and Bases," incorporated herein by reference. If an additive acid is employed, it is preferred it be compatible with the base fuel, the metallic and have low toxicity, low corrosivity, and be as envimomentally friendly as possible.
Naturally, acidic fuel components, which are indigenous to the fuel composition, e.g. base fuel, ECS metallic, ECS oxygenate, or an additional co-combustion catalyst, or ECS component (e.g. aldehydic acids, ketonic acids, carboxylic acids, hydroxyacids, orthoacids, formic acids, and the like) should be ultilized to achieve target pH's, prior to addition of an additive acid.
Individual circumstances will dictate proper approach and additive. Acidic metals of this invention may be used individually andlor in conjunction with one or more other metallics to reduce pH. Non-limiting examples of such acidic metallics include binary, ternary and higher metallic acid salts, hydroxy acids, phosphoric acids, etc., oxamic acid, lithium acetate acid, lithium salt acetic acid, propanoic acid lithium salt, cyclohexanebutyric acid lithium salt, aminobenzole acid lithium salt, borate ester, dimethyl borate, di-n-butyl borate, dicyclohexyl borate, didodecylborate, di-p-cresyl borates, boric acids, orthoborates, phenylboronic acid, diphenylboronic acid, o-tolylboronic acid, p-2 o tolylboronic acid, m-tolylboronic acid, cylohexylboronic acid, cylohexenylboronic acid, cyclopentylboronic acid, methylphenylboronic acid, methylcylohexylboronic acid, methylcyclopentylboronic acid, methylbenzylboronic acid, dimethylphenylboronic acid, dimethylcylohexylboronic acid, dimethylcyclopentylboronic acid, dimethylbenzylboronic acid, diphenylboronic acid, dibenzylboronic acid, dicylohexylboronic acid, dicylohexenylboronic acid, dicyclopentylboronic acid, methyldiphenylboronic acid, bis[(methyl)cylohexyl]boronic acid, bis[(methyl)cyclopentyl]boronic acid, bis[(methyl)benzyl]boronic acid, bis[(dimethyl)phenyl]boronic acid, bis[(dimethyl)cylohexyl]boronic acid, bis[(dimethyl)cyclopentyl]boronic acid, or bis[(dimethyl)benzyl]boronic acid.
Other acidic metallics are set forth below and contemplated.
Example 28 A method of minimizing hydrolysis of a vapor phase combustion fuel composition comprising the steps of:
providing a symmetrical lower dialkyl carbonate;
providing an combustion improving amount of at least one combustible compound containing at least one element selected from the group consisting of aluminum, boron, bromine, bismuth, beryllium, calcium, cesium, chromium, cobalt, copper, francium, gallium, germanium, iodine, iron, indium, lithium, magnesium, manganese, molybdenum, nickel, niobium, phosphorus, potassium, palladium, rubidium, sodium, tin, zinc, praseodymium, rhenium, silicon, vanadium, strontium, barium, radium, scandium, yttrium, lanthanum, actinium, cerium, thorium, titanium, zirconium, hafnium, praseodymium, protactinium, tantalum, neodymium, uranium, tungsten, promethium, neptunium, samarium, plutonium, ruthenium, osmium, europium, americium, fiodium, iridium, gadolinium, curium, platinum, terbium, berkelium, silver, 1o gold, dysprosium, californium, cadmium, mercury, holmium, titanium, erbium, thulium, arsenic, antimony, ytterbium, selenium, tellurium, polonium, lutetium, astatine, mixture thereof, including their organic and inorganic derivative compounds;
providing a hydrocarbon;
mixing said carbonate, said combustible compound, and said hydrocarbon so as to produce a fuel composition having a pH of from 4.5 to 9.5, and store said composition at a temperature of no more than 90°F for up tp 6 months, or longer, and, 2o combusting said fuel in an engine or combustor, wherein vapor phase composition occurs characterized as having a luminous reaction zone extends from surtace of said element.
Example 29 The method of Example above, wherein said fuel is stored at an average temperature of 65EF for 6 months, prior to combustion.
Example 30 A method of mitigating handling hazards of an alkali/alkali earth metal 3 o based vapor phase combustion fuel composition, comprising the steps of:
providing an combustion improving amount of a combustible compound containing at least one element selected from an alkali metal or alkali earth metal, and mixture; and a stabilizer.
3 5 Example 30A
The method of example 30, optionally providing an acidic ECS
metallic; and optionally providing a hydrocarbon; and optionally providing an ECS oxygenate; and mixing said composition.
5 Example 30B
The method of examples 30, 30A, wherein the composition's target pH
ranges up to 9.5.
Example 30C
10 A method of mitigating handling hazards of an alkalilalkaii earth metal based vapor phase combustion fuel composition, comprising the steps of:
providing an combustion improving amount of at least one combustible compound containing at least one element selected from an alkali metal or alkali earth metal; and 15 optionally providing an acidic ECS metallic; and optionally providing a hydrocarbon; and optionally providing an ECS oxygenate, and mixing said composition, said combustible compound, and said hydrocarbon so as to produce a fuel composition having a pH of from 4.5 to 2 0 9.5, and combusting said fuel in an engine or combustor, wherein vapor phase composition occurs characterized as having a luminous reaction zone extends from surface of said element.
2 5 Example 31 The above example 30, wherein the target pH is ranges from 6.0 to 8Ø
Example 32 3o The above example 30, wherein the target pH is achieved by providing at least one acidic ECS metallic or acidic ECS oxygenate.
Example 33 35 The above example 30, wherein the acidic ECS metallic is a phosphorus derivative.

Anhydrous fuels or substantially anhydrous fuels are contemplated and particularly preferred when employing water reactive group la, Ila, Ilb, IIIA
metals and derivative compounds. Circumstances where hydrocarbon bases require anhydrous compositions are contemplated, e.g. jet aviation applications, etc.
Although anhydrous fuels are preferable, fuel compositions of the present invention may contain water.
It is noted, acidity level of Applicant's fuels may be measured in terms of equivalents, e.g., equivalents of KOH required to neutralize the fuel l0 composition. The fuels of the present invention show improved operation at acidity levels which are 100%, 150%, 200%, 300%, or more, above such standards. Acidity levels below such standards, including those at least 50%
less, are expressly contemplated.
Also by way of example, when the fuel compositions of the present invention are used in jet turbine engines, such fuels typically must meet ASTM D 1655 specifications (incorporated herein by reference) or other international specifications, including maximum acidity levels ASTM D 3242 and IP 354 standards. However, it is believed that the increased efficiency of the fuels of the present invention are less destructive to engines during 2 o combustion, and operation with lower pH's than presently acceptable.
International, industry and government fuel standards, including ASTM, IP, GOST, DERD, MIL, AN, U.S. Clean Air Act, California Air Resources Board, and SwedishlEuropean EPEFET standards, etc., governing hydrocarbon fuels containing applicant's ECS oxygenateslmetallics are incorporated herein 2 5 by reference.
It is an embodiment, especially when employing DMC, to maintain a pH in the desired target range and store said fuel at temperatures at or below 90° F.
3 o Example 34 A method of maintain fuel stability, said method comprising:
mixing a fuel composition containing an ECS metallic and a dialkyl carbonate (preferably DMC), and adjusting pH of the fuel composition to less than 10.5 pH.
In addition to the preferred pH ranges described above, it is further contemplated that Applicant's pH adjusted hydrocarbon based fuels will additionally contain known additive, including but not limited to antioxidants, co-solvents, metal deactivators, detergents, dispersants, corrosion inhibitors, mutual solvents, oxygenated anti-knock compound (e.g. hydrocarbyl ethers, alcohols, etc.), conventional combustion catalysts including ferrous picrate, Li and LH promoters, other additive, and additive set forth in incorporated PCT
Applications. The metal deactivators contemplated in this invention are known in the art and incorporated herein by reference.
A preferred fuel of the present invention comprises 1 ) dimethyl carbonate or dimethyl carbonate, representing 0.1 % to 99.5% wt of composition; 2) at least one metal as set forth below, representing 0.01 % to 99.5% wt of composition; optionally a metal deactivator representing 0.00001 % to 10.0% wt of composition, or an antioxidant representing 0.00001 % to 10.0% wt, or a detergent/dispersant representing 0.00001 % to 10.0% wt, or an ignition promoter representing 0.000001 % to 20.0% wt, or a demuisifier representing 0.00001 % to 10.0% wt, or a co-solvent or salt representing 0.000001 % to 40.0% wt, or a hydrocarbon representing 0.1 % to 99.0% volume of the composition, or a co-combustion catalyst (described below) representing 0.000001 % to 80.0% wt, or mixture. Said fuel is constructed with a pH no greater than 11.0 or 10.5, and preferably less than 9.5. More preferably, the pH is from 6.3 to 6.8. When such fuel is a jet aviation turbine hydrocarbon based-fuel, preferred acidity does not exceed equivalent of 0.1 mg KOHIg.
As described in the aforementioned PCT applications, the presence of a co-solvent is also preferred, so long as pH is maintained. Co-solvents that enhance mutual solubility of fuel components, fuel stability, water tolerance are preferred (e.g. C1 to C12 alcohols, alkanolamines, etc.). These are known in the art and incorporated herein by reference. Additionally, co-solvents that increase flash point or reduce vapor pressure are contemplated. Non-limiting examples include, ethanetriols, propanetriols, butanetriols, 1,2,3 butanetriol, pentanetriols, 1,2,3 pentanetriol, 2,3,4 pentanetriol, hexanetriols, septanetriols, octanetriols, or tertraethylene glycol, triethylene glycol, 1-octene, high flash point ketone, naphthalenes, triethylene glycol, trimethylene glycol, isopropyl acetone, diisopropyl acetone, diisopropyl diacetone, diethylene acetate, diethylene diacetate, ethylene acetate compound, phenol, or other flash point temperature reducing co-solvent set forth in aforementioned PCT Applications. Co-solvents should not be corrosive or hazardous to fuel systems.
It is desirable the resultant fuel be constructed to have an average latent heat of vaporization (LHV) no less than typical industry standards.

Preferred LHV's are generally greater. For example, the latent heat of vaporization or enthalpy of vaporization ("apH(Tb)IkJ mol-') for commercial grade diesel, gas turbine, or fuel oils range from about 90 to 105 btullb (at 60°F) or 18 to 21 jK/mole or (at boiling temperatures). Likewise, commercial motor gasolines have a LHV ranging from 135 to 145 btullb or 27 to 29 jKlmole, aviation gasolines about 130 to 150 btullb or 26 to 30 jklmole, and aviation jet fuels about 105 to 115 btulfb or 21 to 23 jKlmole.
Thus, it is preferred that the LHV for commercial grade diesel, gas turbine, or fuel oils at 60°F exceed 105 btullb or 21 jKlmole (at boiling 1o temperatures), for commercial motor gasolines LHV's should exceed 145 btullb or 29 jKlmole, for aviation gasolines LHV's should exceed 150 btullb or 30 jklmole, and for aviation jet fuels LHV's should exceed 115 btu/lb or 23 jKlmole. LHV's at least 2%, 5%, 10%, 20%, 30% or greater than these amounts are however preferred.
The burning velocities {as measured by laminar Bunsen burner flame) for commercial grade diesel, gas turbine, and fuel oils range from about 32-34 cmlsec, kerosine about 36 cmlsec, benzene about 44, automotive gasoline about 44-46 cmlsec, aviation gasoline about 44-45 cmlsec, aviation jet fuels about 32-34 cmlsec. Methanol is reported at about 57 cmlsec.
2 o Thus, in Applicant's fuels it is desireable that burning velocities for commercial grade diesel, gas turbine, and fuel oils exceed 33, 34, 35, 36, 37, 38, 40, 41, 42, 43 cmlsec, kerosine exceed 35, 36, 37, 39, 40, 41, 42, 43, 44 cmlsec, automotive gasoline exceed 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56 cmlsec, aviation gasoline exceed 44, 45, 46, 47, 48, 49, 50, 51, 52, 2 5 53, 54, 55, 56 cmlsec, and aviation jet fuels exceed 35, 36, 37, 38, 39, 40, 41, 42, 43, 44 cm/sec. However, BV's at least 2%, 5%, 10%, 20%, 30%, or greater than the burning velocity of the unadjusted base fuel or conventional fuel is preferred.
It is also desirable that the hydrocarbon based fuels have high possible 3 o allowable densities. High densities of base fuels permit higher concentrations of metallics and dialkyl carbonates. For example, aviation turbine densities equal or exceeding 841 kglma @ 15° C are contemplated. More generally, the fuel compositions of the present invention allow for base fuel densities of from 840 to 1200 kglm3 @ 15° C, and even 900 to over 1200 kgl m3 @
15° C.
35 Moderate, low, to very low densities are also contemplated so long as the increased burning velocity object of above PCT Applications is accomplished and a pH is not greater than 10.5, preferably below 9.0, and most preferably from 6.3 to 6.8 is maintained.

Moreover, highly viscous hydrocarbon fuel bases with viscosities above fuel specification, are unexpectedly brought to within fuel viscosity limits by the addition of dialkyl carbonates and metal. For example, is has been found that a diesel fuel oil having a viscosity of 2.6 mmZIS at 40° C was acceptably combined with dimethyl carbonate representing 5% volume of the composition, and 2.0 grs Mn/gal of methylcyclopentadienyl manganese tricarbonyl (MMT) or alternative non-toxic metallic. The resultant fuel composition had a lower viscosity of 2.4 mm2lS at 40° C.
In this way, highly viscous fuels can be adapted by the addition of applicant's ingredients, whereby non-conforming highly viscous fuels can be made less viscous and brought into compliance with ASTM International, industry and government fuel standards, including ASTM, IP, GOST, DERD, MIL, AN, U.S. Clean Air Act, California Air Resources Board, and SwedishlEuropean EPEFET standards, or other specification (herein incorporated by refererence).
Also by way of example, Jet A hydrocarbon bases having a viscosity of 8.1 to 15.0 or more, (ASTM 445) can be adapted to meet the current 8.0 mm2/s~ at -20°C standard by addition of the components described above.
Alternatively, base fuel viscosity of from 13.5 to 23.0 Cs at -30EF, or more, 2 o may be met by the addition of the components described above.
Similarly, a gas oil turbine hydrocarbon base may have maximum kinetic viscosities at 40°C equal or exceeding 2.45 to 7.0, or greater, mmZls for ASTM D 445 No. 1-GT fuels, and be adapted to meet the 2.4 standard, by addition of the components described herein. Alternatively, base fuel kinetic 2 5 viscosities of 4.15 to 6.0, or more, mrn2/s for ASTM D 445 No. 2-GT fuels, may be adapted to meet the 4.1 standard by addition of applicant=s additives, as described herein.
In an analogous manner, a diesel fuel oil base may have maximum kinetic viscosities at 40°C equal or exceeding 2.45 to 7.0, or greater, mm2/s 3o for ASTM D 445 low sulfur or regular No. 1-D fuels, and be adapted to meet the 2.4 standard by addition of applicant=s additives. Alternatively, a diesel fuel oil base having maximum kinetic viscosities of 4.15 to 9.0, or more, mm2ls for ASTM D 445 low sulfur or regular No. 2-D fuels, and be adapted to meet the 4.1 standard, by addition of applicant=s additives. Similarly, fuels 3 5 having a maximum kinetic viscosity of 24.5 to 60.0, or more, mm2/s for ASTM
D 445 No. 4-D fuels, and be adapted to meet 24.0 mm2ls by addition of applicant=s additives. Additionally, a low emission diesel base may have viscosities exceeding 2.45 to 5.5, or more, cSt at 40°C (where 1 mm2ls =

WO 99/bb009 PCTNS99/13751 1 cSt), and be adapted to meet the 2.4 standard.
Furthermore, a fuel oil base may have kinetic viscosities equal or exceeding 2.15 10.0, or more, mm2ls at 40°C ASTM D 445 for No. 1 fuels, and can be adapted to the 2.1 standard by addition of applicant=s additives.
5 A fuel base having kinetic viscosities of from 3.45 to 10,0, or more, mm2ls at 40°C ASTM D 445 for No. 2 fuels can be similarly adapted to meet 3.4. A
fuel base having kinetic viscosities of 5.55 to 25.0 or more, mm2ls at 40°C
ASTM for D 445 No. 4 fuels (Light), may be similarly adapted to meet 5.5. A
fuel base having kinetic viscosities of from 24.5 to 40.0, or more, mm2/s at 10 40°C ASTM D 445 for No. 4 fuels (regular), may be adapted to meet 24. A
fuel base having kinetic viscosities of from 8.95 to 25.0, or more, mm3ls at 100°C ASTM D 445 for No. 5 fuels (Light), may be adapted to meet 8.9. A
fuel base having kinetic viscosities of from 15.0 to 30.0, or more, mm3ls at 100°C ASTM D 445 for No. 5 fuels (Heavy), may be adapted to meet 14.9.
A
15 fuel base having kinetic viscosities of from 50.5 to 80.0, or more, mm3/s at 100°C STM D 445 for No. 6 fuel oils, and adapted to meet 50.0 mm3ls.
Similarly, a heavy diesel, locomotive or marine engine base fuel, exceeding ISO DIS 8217, BS MA 100, government andlor other industry viscosity specifications, but adapted to meet such standards (incorporated by 2 o reference), typically uncorrected viscosity exceeds such standards by 1.0, 2.0,10.0, 50.0, or more centistokes at 50°C. Applicant has discovered by incorporating his lower dialkyl carbonates and metals, fuels having excessive viscosities can meet government, or other viscosity standards.
By way of further example, an enhanced combustion aviation turbine 2 5 fuel composition of the present invention includes an ECS oxygenate (preferably a dialkyl carbonate andlor dialkyl dicarbonate),.an ECS metal (preferably an alkalilalkali earth metal, or silicon), optionally a co-combustion catalyst, an aviation turbine hydrocarbon base having a viscosity of from 8.1 to 9.0 MM2/S (ASTM 445); optionally one or more of the following: a salt, a 30 co-solvent, antioxidant, freeze point additive, anti-icing additive, metal deactivator, corrosion inhibitor, hydroscopic control additive, lubricity agent, lubricant or friction modifier, anti-wear additive, combustion chamber or deposit control additive, any other recognized additive, additive disclosed in aforementioned PCT Applications, or mixture thereof. The resultant fuel is 35 characterized as being slightly alkaline, substantially neutral or acidic, and having a maximum viscosity equal or less than 8.2 MMZIS~ (ASTM 445). The fuel preferably has a density of from 840.5 to 850, or greater, kglm3 @
15° C, a flash point of at least 38°C, a maximum vapor pressure of 21 kPa @
38°C, minimum thermal stability meeting ASTM D 1655 standards, a heat of combustion or equivalent equal to or exceeding 42.8 MJlkg (lower heats of combustion are contemplated, including those less than or equal to 42.5, 42, 41, 40, 39, 38, 37, 36 MJlkg, based upon additive heats of individual components), and a maximum freezing temperature of from -40 to -50°C, optionally a LHV not less than 115 btullb or 23 jKlmole, optionally a burning velocity exceeding 37 cm/sec.
Example 34A
1o This composition may be summarized as an enhanced aviation turbine fuel composition wherein aviation turbine hydrocarbon base has a viscosity equal or exceeding 8.1 MM2/S, a C3 to C7 symmetrical dialkyl dicarbonate, said fuel optionally characterized as being slightly acidic not exceeding equivalent of 0.1 mg KOH/g.
A diesel fuel, fuel oil, turbine gas oil composition of the present invention includes dimethyl carbonate representing 0.01 % to 40.0% oxygen by weight of the fuel; a compound or element containing a combustion improving amount of transition metal, alkaline metal, alkaline earth, group Illa, IVa, Va, Vla, Vlla element or derivative compound, or mixture, optionally a co-combustion agent, optionally in an concentration of 0.001 to about 100.0 gr elementlgal, preferably 2.0 to 20.0 gr elementlgal; and a No. 1 (ASTM) diesel fuel base having a viscosity of from 2.45 to 3.0, MM2lS at 40°C,; said fuel base optionally characterized as having one or more of the following: a density ranging from 880 to 800 kg/m3 , a cetane index of 40 to ?0, an aromatic content by vol. ranging from approximately 0 to 35%,preferably 0%
to 10%, provided that 3-ring + aromatics not to exceed 0.16 volume %; a T10 fraction temperature of about 190 to 230°C, a T 50 fraction temperature of about 220 to 280°C, a T90 fraction of about 260 to 340°C, a cloud point temperature of °C -10, -28, -32 or 6°G above tenth percentile minimum 3o ambient temperature, a sulfur content preferably not greater than 250 ppm, more preferably not greater than 50 ppm, most preferably not exceeding 5 ppm, a Bunsen laminar burning velocity of at preferably greater than 37, more preferably greater than 44, most preferably 50 ore more, cmlsec, a latent heat of vaporization of preferably at least 105, more preferably at least 120, most preferably 130 or more, BTUIIb. The resultant fuel is characterized as having a pH less than 10.5 and a viscosity equal to or less than 2.4 MM2lS at 40°C, optionally a LHV at 60°F equal or in excess of 105 btullb or 21, 22, 23, 25, 27 jKlmole (at boiling temperatures), optionally a minimum laminar Bunsen burner flame of 37, 39, 40, 41 cmlsec.
Example 34B
A composition, wherein the fuel composition is a diesel fuel oil, the ECS oxygenate is dimethyl carbonate representing 0.01 % to 40.0% oxygen by wt. of the fuel, the hydrocarbon base fuel has a viscosity equal to or greater than 2.5, MMZIS at 40°C, and the fuel composition is characterized as having a pH less than 10.5 and a viscosity equal to or less than 2.4 MM2/S at 40°C.
An aviation gasoline fuel composition of the present invention includes an ECS oxygenate (preferably a hydrocarbyl ether, including MTBE, ETBE, etc.) andlor dialkyl carbonate, an ECS metal {preferably an alkalilalkali earth metal, or silicon), optionally a co-combustion catalyst, and an aviation gasoline base. The resultant fuel is characterized as having a pH less than 7.0 and a minimum octane or performance number of from 87 to 130 (ASTM
909). It is further characterized as having a distillation fraction wherein the sum of the T-10 plus T-50 fractions are 307° F, the T-40 temperature is 167°
F and the T-90 temperature is less than 250° F, a maximum sulfur content of 2 0 0.05 wt%, or sulfur free, a latent heat of vaporization preferably exceeding 120, more preferably exceeding 150, most preferably exceeding 160 BTUIIb, a laminar bunsen burning velocity preferably equal to or in excess of 40, more preferably greater than 48, most preferably greater than 52 cmlsec, a heat of combustion (as measured by the sum of fuel ingredients) equal or less than 43.0 kJlkg, or equal or less than from 18,720 to 15,000, or less, BTUIIb.
Examale 34C
A gasoline composition of the present invention includes an a hydrocarbyl ether (MTBE, ETBE, etc.) andlor dialkyi carbonate, an ECS metal (preferably an alkalilalkali earth metal, or silicon), optionally a co-combustion catalyst, and an unleaded base fuel composition. The resultant composition is characterized as having a pH less than 10.5, and optionally being phosphorus free hydrocarbons, a maximum Reid Vapor Pressure of from 6.0 to 12.0 psi, 6.0 to 10 psi, 6.0 to 9.0 psi; a maximum of 12% to 5.0% by volume, or less of olefins, a maximum of 30% to 20% or less by volume of aromatics (more preferably 15% to 10%, or less), a maximum of 2.0% to 0.8% or less benzene, a maximum of 40 ppm sulfur, most preferably sulfur free, a total 02 concentration ranging of 0.5% to 10.0% wt of dimethyl WO 99!66009 PCT/US99/13751 carbonate, a manganese tricarbonyl compound at 1/64 to 3116 gr. Mnlgal (preferably 1132 gr. Mn) or other metallic in a combustion improving amount, a maximum T-90 temperature of 330°F to 280°F, a T-50 temperature of approx.
170°F to 230°F., 175°F preferred, a minimum (R+M)12 octane of 85, to 92, a bromine number of 20 or less, an average latent heat of vaporization of 880 to 920, or more, BTU/gal at 60°F; a heating value greater than 106,000 btu/gal at 60°F (more preferably greater than 108,000, 114,000 btulgal), as measured by the sum of individual fuel substituents.
1 o Example 34D
A fuel composition, wherein said composition is a gasoline comprising an ECS oxygenate selected from MTBE, ETBE, DMC, or ethanol, characterized as having a pH ranging form 8.5 to 5.5, optionally a maximum Reid Vapor Pressure of 12.0 psi or 8.0 psi, a maximum of 12% voi. olefins, a maximum of 30% vol. aromatics, a maximum of 1.0% vol. benzene, a maximum of 50 ppm sulfur or sulfur free, a total 02 concentration ranging from 0.5% to 4.0% wt of the composition, a maximum T-90 temperature of 330°F to 280°F, a T-50 temperature of approx. 170°F to 230°F., a minimum (R+M)/2 octane of 85, to 92, a bromine number of 20 or less, an average 2 0 latent heat of vaporization of 880 to 920 BTU/gal at 60°F, a heating value greater than 106,000 btu/gal at 60°F.
Example 34E
Another gasoline composition of the present invention includes an ECS
2 5 oxygenate (preferably a dialkyl carbonate andlor dialkyl Bicarbonate, MTBE, ETBE, Ethanol, or methanol), an ECS metal (preferably an alkalilalkali earth metal, or silicon), optionally a co-combustion catalyst, and an unleaded base fuel composition, characterized as having a pH less than 10.5, and optionally characterized as having one or more of the following: being phosphorus free 3o hydrocarbons, with a maximum Reid Vapor Pressure of 12.0 psi, a maximum of 12% olefins, a maximum of 30% aromatics, a maximum of 2.0% benzene, a maximum of 50 ppm sulfur or sulfur free, a total O2 concentration ranging from 0.5% to 10.0% wt of dialkyl carbonate, a combustible metal or non-metal selected from groups set forth below including (but not limited to) those 35 consisting of the preferred manganese, silicon, potassium, and iron compounds, or mixture, a maximum T-90 temperature of 330°F to 280°F, a T-50 temperature of approx. 170°F to 230°F., a minimum (R+M}l2 octane of 85, to 92, a bromine number of 20 or less, an average latent heat of vaporization of 880 to 920 BTU/gal at 60°F, a heating value greater than 106,000 btulgal at 60°F (as measured by the sum of individual fuel substituents), a burning velocity exceeding 50 cmlsec, a latent heat of vaporization exceeding 29 jKlmole (or equivalent).
Example 34F
A similar gasoline composition comprises an ECS oxygenate selected from MTBE, ETBE, DMC, or ethanol, is characterized as having a pH ranging form 8.5 to 5.5, and optionally with a maximum Reid Vapor Pressure of 12.0 1 o psi or 8.0 psi, a maximum of 12% olefins, a maximum of 30% aromatics, a maximum of 1.0% benzene, a maximum of 50 ppm sulfur or sulfur free, a total 02 concentration ranging from 0.5% to 4.0% wt of the composition, a maximum T-90 temperature of 330°F to 280°F, a T-50 temperature of approx.
170°F to 230°F., a minimum (R+M)/2 octane of 85, to 92, a bromine number of 20 or less, an average latent heat of vaporization of 880 to 920 BTUlgal at 60°F, a heating value greater than 106,000 btulgal at 60°F.
Example 34G
Another gasoline composition would include the aforementioned ECS
oxygenates and an ECS metallic (including a combustible alkalilalkali earth metal, preferably a potassium derivative, and MTBE, ETBE, ethanol, methanol, DMC, or EMC, or substitutes as provided herein), and a gasoline base, wherein the resultant composition has one or more of the following characteristics: a RVP of 6.4 to 10.0 psi, aromatics content of 0% to 50%, more preferably no greater than 22%, 25%, 30%, or 35% vol., a benzene content of 0% to 2.0%, preferably no greater than 0.8%, 1.Q%, 1.2% vol., an olefin content of 0% to 25%, preferably no greater than 15%, 12%, 10%, 8%
vol., an distillation evaporation point where 30% to 70% of the fuel has distilled by 200°F, an distillation evaporation point where 70% to 100%
of the fuel has distilled by 300°F, a T50 distillation temperature ranging from 200°F
to 220°F, maximum T90 distillation temperature of 290°F to 310°F, oxygen by wt% ranging from 0% to 5.0%, 0.001 % to 4.0%, 0.1 % to 4.0% to preferably 1.8% to 2.2%., sulfur, ppm, wt. ranging from 0 to 500 ppm, more preferably 30 to 80 ppm.
Example 34H
Another gasoline composition would include the aforementioned gasoline composition, wherein the resultant composition has one or more of the following characteristics: a maximum summer RVP of 8.1, 8.0, 7.5, 7.2, 7.1, 7.0 psi, maximum aromatics of 22%, 25%, or 30% vol., max, benzene of 0.8%, 1.0%, 1.2% vol., T50 distillation temperature ranging from 200°F
to 220°F, a maximum T50 distillation temperature ranging from 200°F
to 220°F, 5 minimum T50 distillation temperature greater than 175°F, maximum T90 distillation temperature of 290°F to 310°F, oxygen by wt% 1.8%
to 2.2%., sulfur, ppm, wt. 30 to 80.
Example 35 10 A gasoline composition including a combustion improving amount of potassium ethoxide and an ECS oxygenate selected from MTBE, ETBE, ethanol, DMC, or EMC, wherein the composition has one or more of the following characteristics: a RVP no greater than 7.5, 7.1, 7.0 psi, maximum aromatics of 22%, 25%, or 30% vol., max. benzene of 1.0% vol., a minimum 15 T50 distillation temperature ranging of 175°F, maximum T90 distillation temperature of 290°F to 310°F, oxygen by wt% 1.8% to 2.2%., and a sulfur content of 0 to 80 wt. ppm, 30 ppm or less preferred.
The invention achieves unexpected reduction of nitrous oxides in 2o combustion after emissions pass through a catalytic exhaust converter. As noted above, reductions of nitrous oxides is important for purpose of reducing global warming gases, but catalytic converters tend to increase the amount of said oxides during their catalytic activity. Applicant has discovered that combusting his ECS oxyenate andlor metallic containing fuels, particularly 2 5 those containing alkalilalkali earth metals, and emitting them through a catalytic converter, he is able to no only reduce the nitrous oxide flowing into the converter, but is able to reduce total oxides, which otherwise would be emitted from the converter. Thus, reducing the harmful effect the exhaust catalyst has in increasing nitrous oxides.
Example 36 A method of reducing green house nitrous oxide gases, comprising:
mixing a combustion improving amount of a combustion improving amount of an ECS metallic, optionally a combustion improving amount of an ECS oxygenate, together with a gasoline; and combusting resultant fuel composition in an automotive engine; and exhausting resultant emissions through an exhaust catalyst; emitting catalyst reacted emissions into the atmosphere; whereby exhaust nitrous oxide emissions are reduced.

Example 37 The Example above, wherein the ESC metal is an alkali or alkali earth metal (preferably a potassium derivative) and the oxygenate is MTBE, ETBE, ethanol, methanol, DMC, and wherein the fuel optionally contains a co-combustion catalyst.
Example 38 The Example of 36, wherein also mixed into the composition is a co-combustion catalyst.
Example 39 The Example of 36, wherein said method incorporates mixing a metal only.
Example 40 The Example of 36 or 39, wherein said metal is absent manganese.
2 0 Example 41 The Example of 36, wherein said fuel composition is includes a combustible alkalilalkafi earth metal, and an ECS oxygenate selected from MTBE, ETBE, ethanol, methanol, DMC, EMC, and mixture, having one or more of the following characteristics: a RVP of 6.4 to 10.0 psi, aromatics content of 0% to 50%, a benzene content of 0% to 2.0%, an olefin content of 0% to 25%, an distillation evaporation point where 30% to 70% of the fuel has distilled by 200°F, an distillation evaporation point where 70% to 100%
of the fuel has distilled by 300°F, a minimum T50 distillation temperature of 175°F
and a maximum T50 distillation temperature ranging from 200°F to 220°F, 3o maximum T90 distillation temperature of 290°F to 310°F,a co-combustion catalyst, oxygen by wt% ranging from 0.1 % to 4.0%, sulfur, ppm, wt. ranging from 0 to 500 ppm; or a fuel composition of the character of Examples 34A
through 34E and 35.
Example 42 The Example of 36 to 41, wherein the fuel composition has a pH
ranging from 10.0 to 4Ø, more preferably 9.0 to 5.0, 8.0 to 6.0, 7.7 to 6.3, or 6.9 to 6.3, or other range or amount set forth herein.

Example 43 The above examples additionally containing an nitrogen based enhancer, or compound containing nitrogen, a nitrogenloxygen combination, or a NH, NH2, NH3, NH4, NO, NN, OON, OONH, ONH, ONH2, ONH3, ONH4, CON, CONH, CONH2, CONH3, COON, COONH, MNH, MON, MONH, MONH2, MONH3, MOON radical (where M is a metal as set forth herein). Non-limiting examples also include fuel soluble andlor combustible amines, amides/imides, such as vitro compounds, nitric compounds, 1 o tetranitromethanes, nitromethanes, nitroethanes, nitropropanes, nitrous oxides, dinitrous oxides, nitric oxides, nitrates, and di-nitrates. Other non-limiting examples include, alkylmetallicamides, polyalkylmetallicamides, alkylphosphoramides, polyalkylphosphoramides (e.g.
hexamethylphosphoramide, hexamethylphosphorus diamide, hexamethylphosphorus triamide, hexamethylphospophorimidic triamide, triethylphosphoramide, trimethylphosphoramide, tripropylphosphoramide, triisopropylphosphoramide, tributylphosphoramide, triisobutylphosphoramide, tri-sec-butylphosphoramide, tri-tert-butylphosphoramide, triphenylphosphoramide, dimethoxyphosphorusamide (CH30)2PNH2), 2 0 diethoxyphosphorusamide, dipropoxyphosphorusamide, diisopropoxyphosphorusamide, dibutoxyphosphorusamide, di-isobutoxyphosphorusarnide, di-sec-butoxyphosphorusamide, di-tert-butoxyphosphorusamide, diphenoxyphosphorusamide, dimethylphosphor-amide (CH30)2PONH2), diethylphosphoramide, dipropylphosphoramide, diisopropylphosphoramide, dibutylphosphoramide, diisobutylphosphoramide, di-sec-butylphosphoramide, di-tert-butylphosphoramide, diphenylphosphoramide, dimethylethylphosphoramide, diethyimethyl-phosphoramide, dipropylmethylphosphoramide, diisopropylmethyl-phosphoramide, di-butyl-methylphosphoramide, di-iso-butylmethyl-phosphoramide, di-sec-butylmethylphosphoramide, di-tert-butyl-methyiphosphoramide, diphenylmethyl phosphoramide).
Phosphoramides are particularly desired.
In the practice of this invention it is contemplated at least one combustible reactive non-lead transition metal, alkaline metal, alkaline earth, group Illa, IVa (except carbon), Va, Vla (except oxygen), Vlfa element, or derivative thereof, as set forth herein, or mixture (herein referred to as "metal"
or "metallic") be together with at least one C3 to C13 symmetrical dialkyl ester of carbonic acid, and mixture, in a fuel stable composition; said composition optionally containing a combustion catalyst as set forth below, a hydrocarbon, andlor an oxidizer; resultant composition as having a pH slightly alkaline, neutral or acidic.
Non-limiting examples of suitable dialkyl carbonates include, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, diisopropyl carbonate, dibutyl carbonate, diisobutyl carbonate, ditertiary butyl carbonate, diisoamyl carbonate, methyl ethyl carbonate, diphenyl carbonate, or mixture. C3 to C8 symmetrical dialkyl carbonates are more desirable, with C3 to C5 being preferred. It is contemplated that such carbonates will be introduced into the l0 composition in concentrations of 0.01 to 100.0 volume percent in an amount sufficient to improve combustion. The carbonates may be additionally combined with one or more oxygenated compounds, including but not limited to alkyl butyl ethers (e.g. MTBE, ETBE, TAME, ETAME, etc.), alkyl alcohols, and/or known co-solvents. In the practice of this invention methylal, ethylal, C1 to C6 aliphatic alcohols, may be substituted for dialkyl cartaonates, absent compromise of vapor phase combustion. Examples of ECS compounds are presented in the aforementioned PCT Applications.
Non-limiting examples of the optional hydrocarbon bases contemplated herein, include any hydrocarbon, including but not limited to carbonaceous liquid or solid fuels, alternative fuels, gaseous fuels (including hydrogen, natural gas, methane, ethane, propane, butane, etc.), automotive gasolines, diesel fuel oils, heavy diesel fuel oils, aviation gasoline, gas oils, fuel oils, aviation jet turbine oils, coal, coat oils, coal liquids, and the like.
Industry specifications, including ASTM, IP, GOST, DERD, MIL, AN, U.S. Clean Air 2 5 Act, California Air Resources Board, and SwedishlEuropean EPEFET
standards, EU Standards, and other reported industry or government standards known in the art, and Criteria for Quality of Petroleum Products, J.P. Allison, 1973 (and subsequent editions), all hereby incorporated herein by reference.
METALS PRACTICE
In the practice of this invention, as set forth in the aforementioned PCT
Applications, contemplated metallics include all non-lead metals, metalloids, and non-metals (herein "metals" or "metallics"}, their derivative compounds 3 5 (organic or inorganic}, whose combustion product accomplishes primary object of vapor phase combustion, which is evidenced by a brilliant luminous reaction zone extending some distance from the metal's surface. Such combustion does not take place on the surface of the metal, or on andlor within the molten layer of oxide covering the metal, typical of heretofore metallic combustion. Distinguishing vapor phase combustion is that its combustion is expansive with elevated exhaust velocities, and resultant metallic oxide particles are formed in the submicron range. Typically fuel economy, power output, exhaust emissions, combustion temperatures are materially improved.
Thus, a very wide range of acceptable metals and derivative compounds are contemplated. Group IA (alkali metals), IIA (alkaline earths) elements, the transition elementslmetals of group Illb, IVb, Vb, Vlb, Vllb, Vlllb l0 [8, 9, 10), the elements of group Ib, Ilb, Illa, IVa (absent carbon), and group Va, Vla, Vlla elements are contemplated. Non-limiting examples include aluminum, boron, bromine, bismuth, beryllium, calcium, cesium, chromium, cobalt, copper, francium, gallium, germanium, iodine, iron, indium, lithium, magnesium, manganese, molybdenum, nickel, niobium, phosphorus, potassium, palladium, rubidium, sodium, tin, zinc, praseodymium, rhenium, silicon, vanadium, strontium, barium, radium, scandium, yttrium, lanthanum, actinium, cerium, thorium, titanium, zirconium, hafnium, praseodymium, protactinium, tantalum, neodymium, uranium, tungsten, promethium, neptunium, samarium, plutonium, ruthenium, osmium, europium, americium, rhodium, iridium, gadolinium, curium, platinum, terbium, berkelium, silver, gold, dysprosium, californium, cadmium, mercury, holmium, titanium, erbium, thulium, arsenic, antimony, ytterbium, selenium, tellurium, polonium, lutetium, and astatine, including their organic and inorganic derivative compounds, which are capable of vapor phase combustion, are contemplated in the claims hereto and incorporated herein by reference. Applicant's metals, including derivative compound, may be organo-metallic or inorganic. Accordingly, the inorganic and organic compounds of CRC Handbook of Chemistr~r and Ph~rsics, Lide, 75th (1994-1995) and earlier editions, Ann Arbor, CRC Press;
Sigma-Aldrich Chemical Directory, Aldrich Chemical Company (1997), Chemical Abstract Service~CAS), on line Registry File [1], American Chemical Society, Chemical Abstract Service, Ohio State University, A
Manual of Inorclanic Chemistry, Thorpe, N.Y., Putnam & Son's (1896), Inor4anic Materials, 2 ed., Ducan, N.Y. J.Wlley 8~ Son (1996), Handbook of Inorganic Compounds, Peny, Phillips, CRC Press, Boco Raton, (1995), Inorganic Chemistry, Phillips, Wllliams, N.Y. Oxford University Press (1965-1966), Inorganic Materials Chemistry, D. Seneeta, G.E. R & D Center, N.Y., CRC Press (1997), _Inorganometallic Chemistry, Fehlner, N.Y., Plenum (1992), Nontransition-Metal Compounds, Eisch, N.Y., Academic Press (1981 ), Metal & Metalloid Amides, Horwood, N.Y., Halsted Press (1980), Kirk-Othmer Encycloaedia of Chemical Technology, 2nd and subsequent editions, John Wiley & Sons (1963), Dictionary of Chemical Names & Synonyms, Howard, Neal, Lewis Publishers, Ann Arbor, {1992), Hawley's Condensed 5 Chemical Dictionary, 12th Edition, Richard J. Lewis, Sr., Van Nostrad Reinhold Company, N.Y. {1993), Dictionary of Chemical Solubilities.
Inorganic, Convey, MacMiilian Press (1921 ), Solubilities of Inorganic and Metal Organic Substances, Seidell, N.Y., Van Nostrand (1940-1941 ), Solubility of Inorganic and Metal-Organic Compounds, Like, Princeton N.J., 10 Van Nostrand (1958-1965), Or anometallics (cite omitted}, Oraano Metallic Chemistry, F.G.A. Stone, Academic Press (1972 and subsequent years), Oraano Metallic Compounds. 2 Ed, Michael Dub, Springer-Verlag, New York Inc. (1966 Vol. 1 to 3, and subsequent volumeslsupplments}, Oraano-metallic Compounds, Coates, Edward, New York, Wiley (1960), Comprehensive 15 Org~anometallic Chemistry II (A Review of the Literature 1982-1994), Abel, Stone, Wilkinson, EI Sevier Science Ltd {1995}, Handbook of Oraanometallic Compounds, Kaufman, D. Van Nostranl Company Inc. (1961 ), Handbook of Oraanometallic Compounds, Hagihara, Kumanda, Okawars, W.A. Benjamin Inc (1968), Oraanometallic Chemistry, Mehrotra, Singh, John Wiley and Sons, 20 (1991 ), Organometallic Chemistry, Chemical Society {1971 and all subsequent publications), London, Metal-Organic Compounds, American Chemical Society (1959 to present}, Chemical Abstracts, American Chemical Society, Chemical Abstract Service, Ohio State University, {From 1907 to present), Structure Reports 1913 to 1973 (Metals and Inorganic Compounds), 25 International Union of Crystallography, Bohn, Scheltena & Hellema (volumes 1-40), The Merck Index, 12th Ed., Budavari, O'Neil, Merck Research Laboratories, N.J. {1996), which are capable of vapor phase combustion, together with said publications (including all relatedlsubsequent editions, volumes, supplements, updates, or related publications) are incorporated 3 0 herein by reference.
However, it is an object of this invention to ultilize where possible those ECS metallics which are not nuerotoxic, especially where human ingestion is possible.
In the practice of this invention, cyclomatic compounds are particularly 35 desireable. Non-limiting examples of cyclomatic compounds include compounds with one or more rings systems, including alicyclic or aromatic ring systems. Ring systems which rnay be wholely organic, wholely inorganic, or heterocyclic. Such ring systems may include cyclic borons (bvrazoles), cyclic silanes (silacyclobutane, 2,4,6,8,10-pentamethylcyclopentasilazane, cyclohexasilanes, cyclopropenyl silanes, etc.), cyclic nitrogens (pyrazoles, pyridines, pyrroles, piperazines, imidazals, etc.), cyclic oxygens (benzoyls, furans, pyrans, e.g. tetrahydropyran, pyrones, dioxins, etc,), cyclic sulfurs (thiophens, dithiles, etc.) or other cyclic inorganics. Cyclomatic organic ring systems include saturated rings (cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, etc.), unsaturated rings, rings with one or more multiple or double bonds (cyclohexadiene, cyclopentadiene, cyclotetraene, etc.), aromatic ringslcycloalkyl radicals (phenyl, benzyl, styryl, etc.), fused rings, to fused aromatic rings (naphthls, naphthenates, etc.), fused ring with cyclopentadienyl moiety, rings containing oxygen or a hydroxyl (phenol, etc.).
The disclosed metallic cyclomatics contained in Heterocyclic Chemistry, Katritzy, Boulton, Academic Press (1966 to 1997 all volumes), Benzenoid-Metal Complexes, Zeiss, Wheatley, Winkler, The Ronald Press Co (1966), The Rina Index 2 Ed, Patterson, Capell, American Chemical Society, Reinhold Publishing Corp (1960 and subsequent editions), Ring Enlar eq ment of Organic Chemist, Hesse, VCH Publishers (1991 ), Rinqs. Cluster. and Plymers of Main Group Elements, Cowley, American Chemical Society (1983), which are capable of vapor phase combustion, together with said publications (including subsequent editions, volumes, or supplements), are incorporated herein by reference.
Desireable metal containing cyclomatic compounds are those with cyclic rings having high burning velocities. The higher the burning the velocity, generally the higher the preference. Generally larger rings have higher burning velocities compared to smaller rings. Thus, a cyclooctane ring is generally preferred over cyclohexane, which is preferred over a cyclobutane ring. Saturated rings are normally more preferred over unsaturated rings. The more saturated the ring the more preferred. Thus, cyclohexane is preferred over benzene. Ring systems where the metal is in turn attached to one or more a hydroxyl, carbonyl, an alkyloxy radicals is generally preferred.
Variations to this general rule are expected.
Non-limiting examples of desireable ring systemslcompiexes include:
cyclohexane, cyclohexene, cyclopentane, cyclobutane, cyclopentadiene, phenyl, benzene, and naphthalene. More desireable are cyclohexane, cyclohexene, and cyclopentadienyl. It is contemplated each elemental metal of this invention can be employed in a cyclomatic compound.
Transition metal ring systems are well known in the art and highly desireable. See U.S. Patents Nos. 2,818,416, 3,127,351, 2,818,417, 2,839,552, 2,680,_; 2,804,468; 3,341,311, 3,272,606, 3,718,444), Canadian Patent #1073207, European Patent Application # 93303488.6, pages 6-8 (1993), incorporated herein by reference. As contemplated herein, ring system attachment may be direct or indirect. Attachment may be via molecular bond, ionic bond, coordination bond or other bond known in the art.
Indirect attachment may be via one or more radical or element, or be via other bond as described below or known in the art. See The Chemisty of Orpanometallic Compounds, Rochow, Hurd, Lewis, New York, John Wiley &
Sons, Inc. (latest edition), incorporated by reference.
One or more radicals (including cyclic radicals), side chains, saturated or unsaturated, may be attached to one or more locations on the ring, andlor to one or more locations of each metal. Thus, the metal may contain between one to as many radicals as available valence electrons (oxidation states) permit. See Handbook of Data on Organic Compounds Zed, Weast, Grasselli, CRC (185).
Non-limiting examples of radicals, include organic or inorganic, saturated or unsaturated, or combinations thereof, including: hydrogen (hydride), hydroxyl, hydrocarbyl group radicals, including alkyl radicals (e.g.
methyl, ethyl, propyl, issopropyl, butyl, isobutyl, sec-butyl, tert-butyl, amyl, pentyl, hexyl, etc.), alkyloxy radicals, various positional isomers thereof (e.g.
1-methyl-butyl, 2-methyl-butyl, 3-methyl-butyl, 1,1-dimethyl-propyl, 1,2-dimethyl-propyl, etc.), corresponding straight and branched chain isomers (e.g. hexyl, hepyl, octyl, nonyl, decyl, etc.), alkenyl radicals (ethyl, /1'-propenyl, I_12-propenyl, isopropenyl, etc.), corresponding branch chain isomers thereof, other isomers thereof (e.g. heptenyl, octenyl, nonyl, decenyl, etc.), alkenyloxy radicals, aryl radicals (e.g. phenyl, a-napthyl, b-naphthyl, a-anthryl, b-anthryl, etc.), aryloxy radicals, including monovalent radicals of such aromatics {e.g.
indene, isoindene, acenaphthene, flourene, phenanthrene, naphthacene, chrysene, pyrene, triphenylene, etc.), aralkyl radicals (e.g. benzyl, a-phenyl-ethyl, b-phenyl-ethyl, a-phenyl-propyl, etc.), aralkyloxy radicals, various positional isomers thereof (e.g. derivatives of 1-methyl-butyl, 2-methyl-butyl, 3-methyl-butyl, 1,1 dimethyl-propyl, etc.), corresponding alkyl derivatives of phenanthrene, flourene, acenapthene, etc., alkaryl radicals, (e.g. o-tolyl, m-tolyl, p-tolyl, o-ethylphenyl, etc.), arylalkenyl, cycloalkyl radicals (benzyl, etc.), cycloalkyioxy radicals, aliphatic radicals, mesityl. See generally Canadian Patent 1073207, pages 4-7, European Patent Application # 93303488.6, pages 6-8, 10/11193), Handbook of Data on Oraanic Compounds 2 Ed, Weast, Grasselli, CRC 1985, CRC Handbook of Chemistry and Physics, 75th and earlier editions, sections re: "Nomenclature For Inorganic Ions and Radicals," "Organic Radicals and Ring Systems," Nomenclature of Inoroanic Chemistry (Recommendations, Blackwell Scientific Publications, Offord 1990; Richer, J.C., Panico, R., and Powell, W.H. A Guide to IUPAC
Nomenclature of Organic Compounds, Blackwell Scientific Publications, Offord 1993, Weast, R.C., and Grasselli, J.C., Handbook of Data on Organic Compounds. 2nd Ed. CRC Press, Boca Raton, FL, 1989; incorporated by reference.
Hydroxyl, alkanol, alkanolamine, oxy andlor oxygen containing radicals, including derivatives of thereof and derivative of above radical are also contemplated. Non-limiting examples include hydroxy, methoxide, ethoxide, propoxide, isopropoxide, butoxide, isobutoxide, seo-butoxide, tert-butoxide, pentoxide, amyloxide, phenyloxidesperhydroxy, methoxy, methylol, methylenedioxy, ethoxy, ethyfol, ethylenedioxy, enanthyl, propoxy, proprylol, propylenedioxy, isopropoxy, isopropylol, isopropylenedioxy, butoxy, butylenedioxy, butylol, iso-butoxy, iso-butylol, isobutylenedioxy, isobutyryl, sec-butoxy, sec-butylol, sec-butylenedioxy, tert-butoxy, tert-butylol, tert-butylenedioxy, butyryl, caproyl, capryl, caprylrl, pentoxy, pentylol, pent alenedioxy, amylol, amylenedioxy, phenoxy, phenylol, phenylenedioxy, 2 o phenylmethoxy, diphenylmethoxy, benzoyl, benzyloxy, benzoxy, iso-benzoyl, napthoxy, napthylol, hexylol, hexamethylol, amylenedioxy, hexadecanoyl, heptanedioyl, hexylenedioxy, carbomethoxy, carbethoxy, carbobenzoxy, carbpropoxy, carbisopropoxy, carbutoxy, phenacyl, phenacylidene, propionyl radicals, methyienedioxyl, carbonyldioxy, etc., including derivatives, homologes, analoges, and isomers thereof. Additional non-limiting oxygen containing radicals include acetyl, acetamido, acetoacetyl, acetonyl, acetonylidene, acrylyl, alanyl, B-alanyl, allophanoyl, anisyl, benzamido, butryl, carbonyl, carboxyl, carbazoyl, caproyl, capryl, caprylrl, carbamido, carbamoyl, carbamyl, carbazoyl, chromyl, cinnamoyl, crotoxyl, cyanato, decanoly, disiioxanoxy, epoxy, formamido, formyl, furyl, furfuryl, furfurylidene, glutaryl, glycinamido, glycolyl, glycyl, glyocylyl, heptadecanoyl, heptanolyl, hydroperoxy, hydroxarnino, hydroxylamido, hydrazidolhydrazide, hydroxy, iodoso, isoccyanato, isonitroso, keto, lactyl, methacrylyl, malonyl, nitroamino, vitro, nitrosamino, nitrosimino, nitrosyllnitroso, nitrilo, oxamido, peroxy, phosphinyl, phosphidelphosphido, phosphitelphosphito, phospho, phosphono, phosphoryl, seleninyl, selenonyl, siloxy, succinamyl, sulfamino, sulfamyl, sulfeno, thiocarboxy, toluyl, ureido, valeryl radicals, etc., including derivatives, homologes, analoges, and isomers thereof.

Additional non-limiting examples of other radicals, include: acetimido, amidino, amido, amino, aniline, anilino, arsino, azido, azino, azo, azoxy, benzylidine, benzldyne, biphenylyl, butylene, iso-butylene, sec-butylene, tert-butylene, cyano, cyanamido, diazo, diazoamino, ethylene, disilanyl, glycidyl, guanidino, guanyl, heptanamido, hydrazino, hydrazo, hypophosphite (hypophosphito), imido, isobutylidene, isopropylidene, silyl, silylene, methylene, mercapto, methylene, ethylene, naphthal, napthobenzyl, naphthyl, naphthylidene, propylene, propylidene; pryidyl, pynyl, phenethyl, phenylene, pyridino, sulfinyl, sulfo, sulfonyl, tetramethylene, thenyl, thienyl, thiobenzyl, thiocarbamyl, thiocarbonyl, thiocyanato, thionyl, thiuram, toluidino, tolyl, a-tolyl, tolylene, a-tolylene, tosyl, triazano, ethenyl (vinyl), selenyl, trihydrocarbyiamino, trihaloamino, trihydrocarbyl phosphite, trihalophosphine, trimethylene, trityl, vinylidene, xenyl, xylidino, xylyl, xylylene, 1,3-diene, hydrocarbyl radicals, etc., including derivatives, homologes, analoges, and isomers thereof. Thus, ring compounds or metals themselves may directly or indirectly contain one or more chelating radicals (e.g. carbonyl, cyano, etc.).
One or more of the above radicals may be attached directly or indirectly to another. Indirect attachment may be via one or more intermediate atom, including but not limited to carbon, nitrogen, oxygen, phosophorus, silicon, boron, sulfur, or another metal. Metallic compounds may have one or more non-ring radicals attached. Desireable metals may for example have one or more alkyl, alkylene or similar radical attached to the metal, or one or more hydroxyl, carbonyl, alkyloxy, alkanol radicals, or combination thereof attached. Examples include Other metallic compounds may have one or more ring systems attached directly or indirectly to a metal, with or without an attached non-ring radical to the metal.
One or more cyclic rings maybe attached, fused or indirectly attached together or linked together via one or more radicals, one or more atoms, including but not limited to carbon, nitrogen, oxygen, phosophorus, silicon, boron, sulfur, or a metal.
One or more metals may be attached to each other, for example hexamethyldisilane, which is a preferred metallic. Indirect attachment herein includes attachment via one or more radicals, andlor one or more atoms, including but not limited to carbon, nitrogen, oxygen, phosophorus, silicon, boron, sulfur, or another metal.
As contemplated herein said carbon, nitrogen, oxygen, phosophorus, silicon, boron, sulfur, or other metal atom, may be attached to itself or to another herein, one or more times, with each atom optionally having one or more hydrogen andlor radical(s). Said attachment may be independent of attachment to any other radical or metal, or may include an attachment to another radical or metal.
5 Likewise one or more cyclic rings may be attached directly to the metal, or indirectly via one or more non-ring radicals, andlor via one or more intermediate atoms, including but not limited to carbon, nitrogen, oxygen, phosophorus, silicon, boron, sulfur, or another metal.
Thus, one or more metals may be attached at one, or up to every 10 location possible on the ring system, directly and/or indirectly. Likewise, one or more ring systems may be attached at one, or up to every metal location possible, directly and/or indirectly.
A non-ring radical may be independently attached directly or indirectly to the metal, absent its attachment of a ring system. In the practice of this 15 invention the attachment of one or more non-ring radicals) to a metal, absent a ring system is expressly contemplated.
Contemplated oxygenated metallic compounds include metallic alkanols, ethers, ketones, hydroxides, alkyloxy, including methoxy, dimethoxy, trimethoxy, ethoxy, diethoxy, triethoxy, oxalate, carbonate, Bicarbonate, 2 o tricarbonate, and similar structured compounds, including mixture thereof.
For example trimethoxymethylsilane (as set forth below) is desireable. Metallic carbonates, including dimetallic carbonates, dimetallic Bicarbonates, and the like, are also contemplated. It is contemplated these oxygenated metallic or organo-metallic compounds may be employed absent a dialkyl carbonate or 2 5 other oxygenated ECS structure.
Likewise one or more non-ring radicals may be independently attached directly or indirectly to the ring system, absent attachment of a metal. An independent attachment of a metal may be via intermediate radical, one or more intermediate atoms, including but not limited to carbon, nitrogen, 30 oxygen, phosophorus, silicon, boron, sulfur, or another metal.
A cyclic ringlradicallside chain may be indirectly attached to the metal through one of more atom, including but not limited to carbon, nitrogen, oxygen, phosophorus, silicon, boron, sulfur, or a metal. Indirect attachment via oxygen is contemplated but less desireable.
35 Cyclic rings may be attached to one or more non-ring radicals, atoms andlor ring systems prior to a direct or indirect attachment of the metal. For example, [2-(cyclohexenyl)ethyljtriethoxysilane contains a ethyl radical attached to the cyclohexenyl ring, which is then attached to silicon. This is a preferred metallic structure.

Thus, cyclomatic compounds may contain one or more ring systems, optionally with one or more non-ring radicals attached thereto. Said rings) then may be attached directly or indirectly to a metal, with said metal in turn optionally attached directly or indirectly to a radical, with said radical being optionally a non-ring radical selected from one or more hydrogen, hydroxyl, alkyl, aryl, carbonyl, alkanol, alkanolamine, alkyloxy, oxy or oxygen containing radical. Non-limiting examples include methylcyclopentadienyl manganese tricarbonyl, [2-(cyclohexenyl)ethyljtriethoxysilane, and cyclohexenyl l0 dimethoxymethylsilane.
Another class of desireable metallics include metal hydrides or metallic hydryls. Examples of metallic hydryls include sodium hydride, lithium hydride, aluminum hydride, aluminum borohydride; boron hydride, boron anhydride, beryllium borohydride, lithium borohydride,lithium aluminum hydride, lithium borohydride, sodium borohydride, transition-metal hydrides, transition-metal carbonyl hydrides, transition-metal cyclopentadienyf hydrides, and mixture.
Those hydrides known in the art and those disclosed in Metal Hydrides, Bambakidis, New York, Pienum Press (1981 ), Boron Hydride Chemistr~r, Muetterties, New York, Academic Press (1975), which accomplish primary vapor phase combustion object of this invention, are contemplated in the claims below and incorporated herein by reference.
Organometallic nitrosyls are also desireable. See for example Metal Nitrosvls, Richter-Addo, Oxford University Press, U.K. (1992), incorporated by reference. Flammable metal napthenates or metals derivatives of napthenic acid are desireable, including potassium naphthenate.
Alkalilalkali earth metal carbonates (including organic alkyl aryl carbonates), alkalilalkali earth formates, alkalilalkali earth etherates, alkali/alkafi earth alkalates, alkali/alkali earth esters, multi-metal alkyllalkyl earth carbonates, or carbonates including those with a hydrogen (e.g.
LiHC03, Na2C03, NaHC03, MnC03, MgCO3, CaC03, CaMg(C03)2, etc.), alkali metal carbonates; and other metal carbonates (e.g. AgC03, TI2C03, etc.), including organic derivatives are contemplated. Contemplated salts also include acid salts containing replaceable hydrogen. Double oxides and hydroxides are also contemplated.
Transition metals and their known cyclomatic compounds, including carbonyl compounds are expressly contemplated. See Fundamental Transition Metal Or9anometallic Chemistry, Lukehart, Monteray, Calif, BrookslCole (1985), Transition Metat Compounds, King, New York, Academic Press (1965), Transition-Metal Oraanometallic Chemistry, King, New York, Academic Press (1969), Fundamental Transition Metal Oraanometallic Chemistry, lukehart, Monterey, Ca., Brooks/Cole (1985), incorporated herein by reference. A preferred cyclomatic transition metallic is MMT.
Contemplated herein are non-transition-metal compounds known in the art. See Nontransition-Metal Compounds, Eisch, New York, Academic Press {1981 ), incorporated by reference. Non-transition metal compounds that accomplish primary object of vapor phase combustion are contemplated in the claims below and incorporated herein by reference.
1 o Likewise known metallocenes are contemplated. Non-iimiting examples include alkylmetallocenes, arylmetallocenes, including dicyclopentadienyl-metal with the general formula (C5H5)2M, dicyclopentadienyl-metal halides with the general formula (C5H5)2MX1-3, monocyclopentadienyl-metal compounds with the general formula C5H5MR1-3, where R is CO, NO, halide group, alkyl group, etc. Non-limiting examples include napthacenes, metallocene, ferrocene, methylferrocene, cobaltocene, nickelocene, titanocene dichloride, zirconocene dichloride, uranocene, decamethylferrocene, decamethylsilicocene, decamethyfgermaniumocene, decamethylstannocene, decamethylphosocene, decamethylosmocene, 2o decamethylruthenocene, decamethylzirconocene, sificocene, decamethylsilicocene, etc., are also contemplated. Metallocenes that accomplish primary object of vapor phase combustion are contemplated in the claims below and incorporated herein by reference. See also Hawle s Condensed Chemical Dictionary 12th ed, Lewis, Van Nostrand Reinhold Company, New York (1993), also incorporated by reference.
Carbonyl compounds are expressly contemplated. A limited number of examples include decacarbonyl dimanganese, (acetylacetonato~ii-carbonylrhodium. See for example Carbon~yrlation: Direct Synthesis of Carbon l~pounds, H.M. Colquhoun, Plenum Press (1991 ), incorporated herein by reference.
As noted above, non-limiting non-leaded simple binary/temary metallic compounds, including binaryltemary and higher metallic salts, acid salts, including those with replaceable hydrogen, etc., are contemplated. Hydroxy acids, perchlorates, sulfates, nitrates, carbonates, hydroxides, methylates, ethylates, propylates, and others, are also contemplated. Non-limiting examples include potassium nitrite, sodium nitrite, lithium nitrite, and hexamethylphosphoric triamide.

WO 99/66009 PC'f/US99/13751 It is also within the scope and practice of this invention to employ oxygenated containing ECS metallic compounds, including oxygenated organo metallic compounds, which are metallic alcohols, alkanolamines, ketones, esters, ethers, carbonates, and the like, which are themselves ECS
compounds, in hydrocarbon fuels with or absent additional dialkyl carbonate or other ECS structure. Those metallics are incorporated herein by reference.
Additionally, this invention contemplates one or more similar organo oxygen containing metallics, including mixture, with or without an ECS compound, to act as neat "stand alone" fuel. Thus, it is an express embodiment to use metallic compounds alone, as singular means of enhancing fuel combustion.
However, it is preferred the metallic be added to the ECS oxygenate, preferably MTBE, ETBE, DMC, or Ethanol, optionally a co-fuel, an oxidizer, catalyst, andlor a hydrocarbon. The contemplated oxidizers of this invention are set forth in the aforementioned PCT applications. Oxidizers, including those employed in rocket propulsion, which are known in the art are incorporated by reference.
It is also within the practice of this invention to employ a metallic compound, including homologue, analogue, isomer, or derivative thereof, having a structure or structure similar to 2 0 M-R", R"-M-M-R", R"-M-Q-M-R", R"-M-Q'-M-R", R"-M-R'-M-R", wherein M iS
one or more non-leaded metal(s), metalloid(s), or non-metal element(s), and R is one or more hydrogen, cyclic ring systemlradicallside chain(s), andlor non-ring radicallside chains) as provided herein above, including but not limited to alkyl, aryl, alkyloxy, alkylanol (alkanol), hydroxyl, aryloxy, polyalkyl, polyaryl, polyalkyloxy, polyalkylanol, polyaryloxy, polyhydroxyl radicals. R' is one or more cyclic ring systemlradical/side chain(s), andlor non-ring radical/side chains) as provided herein. If R is greater than 1, then subsequent R's may be same or different radical, etc. R also be a single radical or one radical attached to one or more radicals. "n" is an interger 3o ranging from 1 to the number of valence electrons (or common oxidation states) available of M. Q is an atom having a minimum oxidation available of 2, including but not limited to carbon, nitrogen, oxygen, phosophonrs, silicon, boron, sulfur, or a differing metal than M. Q' is an atom with a minimum available oxidation state of 2, including but not limited to carbon, nitrogen, oxygen, phosophorus, silicon, boron, sulfur, or a differing metal than M, also containing one or more radicals.
Additional oxygenated-organo or oxygenated metallic structure includes M1-O(CO)O-M2, wherein M1 or M2 are the same or different metal or element. M1 may be a double valence cation, wherein M2 is absent from above structure, unless additional carbonate is included. Preferred M
valences are 1 or 2. M valences or multiple M1 M2 combinations having combined valence greater than two are acceptable. In which case, additional carbonate structure would be added, e.g. CaMg(C03)2.
In the immediate structure above, M11M2 valence's may be greater than one, wherein excess valence is occupied by same or additional metal {element), and/or wherein M1 or M2 are substituted for a single or double bond oxygen, andlor by one or more radicals. M1 or M2 also may be 1o substituted for single bond oxygen, or nitrogen, andlor by one or more radicals, including methyl, hydrogen, hydroxy, ethoxy, carbethoxy, carbomethoxy, carbonyl, carbonyldioxy, carboxyl, methyoxy, isonitro, isonitroso, or methylenedioxyl radical. Non-limiting examples include carbonates of lithium [Li202(CO)], ammonium manganese, potassium [K2O2(CO)], sodium, calcium, cesium, copper, rubidium, lithium hydrogen, sodium hydrogen, potassium hydrogen, potassium sodium, magnesium, and the like.
It is contemplated that C2 to C8 metallic ethers, C2 to C41C51C6 metallic ethers being more desireable, will be used as metallic structure in this invention. For example, M'1-CH2-CH2-O-CH2-CH2-M'2 structure is contemplated wherein M'1 and M'2 may be same or different metallic or wherein one M'1 or M'2 may be hydrogen, or other atom, or radical with one available valence.
Other contemplated structure include metallic ketones, esters (esters 2 5 of boric acid), alcohols, acids, and the tike. Non-limiting examples include M'1-C-OH3-R, wherein M'1 is one or more metallic comprising valence of 3 or greater, and R is radical, whereby resulting structure is ketone, ester, acid, alcohol; or ether. Other structure include M'1-C204, wherein M'1 has a valence of 2. M1-C-C-O-C-C-M2 structure is also contemplated wherein M1 3o and M2 may be same or different metallic or wherein M2 may be hydrogen or atom of one valence. Other structure includes RO-M, where RO is an alkanol and M is a metal. Similar structure is contemplated for M have available valence greater than 1.
As in the case of ECS oxygenates, the carbon chains of organo-ECS
35 metallics are preferably shorter than longer. For example, a 5 carbon atom straight chain, which is immediately antecedent to a metal atom, is less preferred than a 4 carbon straight carbon atom chain. A three carbon chain is more preferred over a 4 carbon atom chain, and a two more preferred than a 3. Generally the longer the chain, the less desireable. An exception would be where the chain length and character positively increases burning velocity.
Where there is an intermediate oxygen or nitrogen atom between the carbon chain and the metal atom, particularly if the oxygen or nitrogen atom is 5 attached to the metal, a chain of two carbon atoms is generally preferred over a single carbon atom. In such cases an ethyl radical is generally preferred over propyl, which is preferred over butyl radicals. Branch chains are prefer-ed over straight chains with the same number of carbon atoms.
Chains greater than 10 carbon atoms long are less desireable and not 1o normally contemplated. Thus, the oil soluble metal soap of aluminum stearate, which has three separate 17 carbon chains each connected to the aluminum atom through an intermediate oxygen atom [CH3(CH2)~6COOJ3AL, is not an effective ECS metallic and is excluded. Poorly combustible long chain metal soaps are excluded from the ECS metallics contemplated herein.
15 Also excluded is cety! pyrdrium chloride, Non limiting examples of lithium derivative compounds of this invention, include: lithium bis(dimethylsilyl)amide, lithium bis(trimethyl-silyl)amide, oxamic acid, P-aminosalicylic acid lithium salt, lithium salt 5-nitroorotic acid, lithium D-gluconate, lithium hexacyanoferrate(III) 20 {Li3Fe(CN)6), lithium diphenylphosphide, lithium acetate, lithium acetate acid, lithium salt acetic acid, lithium acetamide, lithium anilide, lithium azide, lithium benzamide, lithium antimonide, lithium orthoarsenate, lithium orthoarsenite, lithium meta-arsenite, lithium diborane, lithium pentaborate, lithium dihydroxy diborane, lithium borohydride, lithium cadium iodide, lithium chloride, lithium 25 calcium chloride, lithium carbide, lithium carbonate, lithium hydrogen carbonate, lithium carbonate, alkyl lithium carbonates, lithium methyl carbonate, lithium ethyl carbonate, lithium carbonyl, lithium cobalt (II) cyanide, lithium cobalt (111) cyanide, lithium cobaltinitrite, lithium cynomanganate (II), lithium cynomanganate (III), lithium citrate, lithium ferricyanide, lithium 3o ferrocyanide, lithium formate, lithium hydride, lithium hydroxide, lithium manganate, lithium permanganate, lithium methionate, lithium napthenate, lithium nitride, lithium nitrate, lithium nitrite, lithium nitrobenzene (e.g.
lithium-p-nitrobenzene), lithium nitrophenoxide, lithium etherate, lithium chromate, lithium oleate, lithium oxalate, lithium oxalatoferrate (II), lithium oxalatoferrate 35 (III), lithium monoxide, lithium oxide, lithium peroxide, lithium mono-orthophosphate, lithium hypophosphite, lithium orthophosphite, lithium hydroxoplumbate, lithium rhodium cyanide, lithium selenide, lithium selenite, lithium selenocynate, lithium selenocyanoplatinate, lithium disilicate, lithium metasilicate, lithium sodium carbonate, lithium sodium ferricyanide, lithium hydroxostannate, lithium disufide, lithium hydrosulfide, lithium pentasulfide, lithium tetrasulfide, lithium trisulfide, lithium telluride, lithium thioarsenate, lithium thioarsenite, lithium trithiocarbonate, lithium thiocyanate, lithium amide, lithium salt (E,E}-2,4-hexadienoic acid, dilithium fluorophosphate, dilithium fluorophosphite, trilithium phosphate, trilithium phosphite, lithium perchlorate, propanoic acid lithium salt, lithium formats, lithium cyanate, lithium hexacyanocobaltate (111), lithium hypophosphite, lithium hexa-flurorsilicate, lithium nitroprusside, lithium phenoxide, lithium phosphate (dibasic, monobasic, tribasic), lithium salicylate, lithium selenide, lithium tetracyanonickelate (II}, lithium tetrafluoroborate, lithium xanthogenate, lithium -p-aminobenzoate, lithium copper ferrocynanide, lithium cupric ferrocyanide, lithium hexafluorophosphate, lithium hexanitricobaltate III, lithium naphthenate, lithium -B-naphthoxide, lithium polysulfide, lithium -sodium phosphate, lithium stearate, lithium sulfide, lithium sulfite, lithium sulfate, lithium thiocyanate, lithium xanthate, lithium fluorosilicate, N-lithiumethylenediamine, oxalic acid dilithium salt, lithium beta-hydropyruvic acid, lithium 1,1-dimethylurea, lithium 1,1-diethyfurea, lithium 1,1-diepropylurea, lithium xanthate, lithium ethylxanthate, lithium methylxanthate, lithium salt thiophenol, lithium triphenylmethyllithium, methyllithium, ethyllithium, lithiumethynyl(acetylide), propyllithium, isopropyllithium, butyllithium, isobutyllithium, secbutyllithium, tertbutyllithium, pentalithium, hexyllithium, heptalithium, amyllithium, isoamyllithium, benzyllithium, dirnethylbenzyl-lithium, tolyllithium, dodecyllithium, cyclopentadienyllithium, methylcycfopentadienyllithium, cyclohexyllithium, lithiumheptyl, Iithiumdodecyl, lithium tetradecyl, lithium hexadecyl, lithium octadecyl, phenyllithium, lithium o-tolyl, lithium m-tolyl, lithium p-tolyl, lithium-p-chlorophenyl, lithium p-bromophenyl, lithium o- anisyl, lithium m-anisyl, lithium p-anisyl, lithium diethoxyphenyl, lithium dimethoxyphenol, lithium m-cumyl, lithium p-ethoxyphenyl, lithium m-dimethylaminophenyl, lithium 9-flourene, lithium a-napthyl, lithium b-napthyl, lithium p-phenylphenyl, lithium 9-phenylanthryl, lithium 9-anthryl, lithium 9-methylphenanthryl, lithium pyridyl, lithium 2-pyridyl, lithium 3-pyridyl, lithium 6-bromo-2-pyridyl, lithium 5-bromo-2-pyridyl, lithium dibenzofuryl, lithium 3-quinoyl, lithium 2-lepidyl, lithium triphenylmethyl, lithium 2,4,6-trimethylphenyl, lithium 2,4,6-triisopropylphenyl, lithium 2,3,5,6-tetraisopropylphenyl, lithium tetrabutylphenyl, thiophenedilithium, toluenedilithium, diphenylethylenedilithium, lithiumamylethynyl, lithiumphenyl-ethynyl, lithiummethoxybromophenyl, lithium phenylisopropyl, lithium tetraphenylboron, lithium tetramethylboron, lithium a-thienyl, lithium m-trifluoromethylphenyl, phenylethynyllithium, 3-furyllithium, phenylisopropyllithium, dibenzofuranyllithium, lithium dimethylbenzyl, lithium selenocyanate, lithium trimethyl-silanolate, diphenylphosphide, lithium benzoate, lithium tert-butyl carbonate, lithium azide, di-lithiumcyanamide, lithium cyanide, lithium dicyanamide, cyclohexanebutyric acrd lithium salt, cyclohexane acid lithium salt, cyclopentadientyllithium, lithium tri-tert-butoxy-aluminum hydride, lithium triethyl-borohydride, lithium trimethylborohydride, lithium tripropyl-borohydride, lithium triisopropylborohydride, lithium tributylborohydride, lithium triisobutylborohydride, lithium tri-sec-butylborohydride, lithium tri-tert-butylborohydride, lithium trisiamylborohydride, lithium chlorate, lithium tert-butoxide, lithium sec-butoxide, iso-butoxide, lithium antimonate, lithium diphenylphosphide, lithium bis(trismethylsilyl) amide, trilithium phosphite, lithium selenocyanate, lithium tri-sec-butylborohydride, lithium triethylsilanotate, lithiumthiocyanate, lithium acetylide, lithium chlorate, lithium salicylate, lithium di-lithium tetracarbonylferrate, lithium tetraphenylborate, lithium triethylborohydride, lithium triacetoxy-borohydride, lithium triphenylborane, lithium hydroxide, lithium diphenylphosphide, lithium methoxide, lithium ethoxide, lithium tri-sec-2 0 butylborohydride, tri-tert-butylborohydride, lithium triethylborohydride, lithium triphenylborohydride, lithium trisiamylborohydride, lithium metavanadate, lithium cyclohexanebutyrate, lithium hexachloroplatinate, lithium thiocyanate, lithium selenocyanate, lithium cyanate, lithium floride, lithium hexafluoroan-timonate, lithium hexafluoroaluminate, lithiumaluminate, lithiumaluminum-tri-tert-butoxide, lithium hexafluoroarsenate, lithium hexafluorosilicate, lithium hexacyanocobalt(ll)ferrate(II), lithium ferrosilicon, dilithiumhexacyanocobalt(li)ferrate(II), lithium hexafluorotitanate, lithium hexafluorozirconate, lithium hexahydroxyantimonate, lithium hexachlororuthenate, lithium hexachloropalladate, lithium formats, lithium tetracyanonickelate, lithium tetrafluoroaluminate, lithium tetrafluoroborate, lithium thioacetate, L-glutamic acid monolithium salt, fumaric acid lithium salt, oxamic acid lithium salt, lithium salt diphenyl-phospane, P-aminobenzoic lithium salt, aminobenzole acid lithium salt, alpha-napthaieneacetic acid lithium salt, dilithium salt 2,6-naphthalenedicarboxlic acid, lithium cyclcohexanetherate, lithium phthalimide, P-aminosalicylic acid lithium salt, lithium salt 3,5-dimethylcyclohexyl sulfate, indolebutyric acid lithium salt,indole-3-butyric acid Lithium salt, diphenylphosphide, lithium dimethyl-silanolate, lithium triethylborohydride, lithium propoxide, lithium isopropoxide, lithium butoxide, lithium sec-butoxide, lithium pentoxide, lithium tert-pentoxide, lithium hydrogenphthalate, lithium oxalate, lithium hydrogensulfate, monolithium acetylenedicarboxylic acid, lithium pyrophosphate, lithium dihydrogenphosphate, lithium hexoate (lithium salt hexoic acid), lithium diphenylphosphide, lithium trimethylsilonalate, lithium phthalic acid, P-aminobenzoic acid lithium salt, monolithium L-aspartic acid, tetraphenyldilithium (C6H5)2CLi2C(C6H5)2, lithiumethylphenyl (LiCH2C6H5), lithium bromate, lithium hydrogenphospate, monlithium salt D-shaccharic acid, DI-asparatic lithium salt, (R}-alpha-hyroxymethylaspartic acid lithium salt, lithium fluoride, lithium iodate, lithium salt ethyl malonate, lithium thioacetate, lithium phenol, lithium salt aminobenzoic acid, lithium aminophenol salt, lithium cyclohexenol, lithium methylcyclohexenol, lithium cyclopropanol, lithium methylcyclopropanol, lithium cyclobutanol, lithium methylcyclobutanol, lithium methylcyclopentanol, lithium cyclopentanol, lithium cyclohexenol, lithium methyicyclohexenol, lithium dimethyicyclohexenols (e.g. lithium 3,5 dimethylcyclo-hexanol, lithium 2,3-dimethylcyclohexanol, lithium 2,6 dimethylcyclohexanol, lithium 2,5-dimethylcyclohexanol, 3,5-dimethylcyclohexanol), lithium o-ethylxanthic acid, monolithium salt 2 ketoglutaric acid, difithium salt, ketomalonic acid, lithium salt lactic acid, 2o dilithium thiosulfate, lithium antimony tartrate, lithium dichloroacetate, lithium dimethylacetate, lithium diethylacetate, lithium dipropylacetate, lithium metaborate, lithium tetraborate, lithium tetrachlorocuprate, lithium acetoacetate, lithium diisopropylamide, lithium diethylamide, lithium dimethylamide, lithium bis(dimethylsilyl)amide, dilithium phthalocyanine, dilithiumtetra-bromocuprate, dilithium tetrabromonickelate, dilithiumtetra-chioromanganate, dilithiumbutadiyne, lithium cyclopentadienide, lithium dicyclohexylamide, lithium diethylamide, lithium dimethylamide, lithium dipropylamide, lithium diisopropylamide, lithium thexylborohydride, lithium tri-tert-butoxyaluminohydride, lithium trimethylsilyl)acetylide, lithium triethylsilyl)-acetylide, lithium tris[(3-ethyl-3-pentyl)oxy]aluminohydride, (phenylethynyl)lithium, 2-thienyllithium, lithium diethyldihydro-aluminate, lithium dimethyldihydroaluminate, lithium aluminum hydride, lithium bifluoride, lithium biphenyl, lithium bis-elenite, lithium bis(2-methoxyethoxy)aluminum hydride, lithium bismuthate, lithium borate, lithium chlorite, lithium cobalt-nitrite, lithium cyanoborohydride, lithium cyclopentadienide, lithium dicyanamide, lithium hexametaphosphate, lithium hexanitrocolbaltate, lithium hydrogenphosphite, lithium hydrogenselenite, lithium hydrogensulfite, lithium hydrosulfite, lithium hypochloride, lithium metaarsenite, lithium metabisulfide, lithium metaperiodate, lithium methacrylate, lithium nitroferricyanide, oxybate, lithium pentamethylcyclo-pentadienide, lithium phenofate, polyphosphate, lithium polypho-sphite, lithium propionate, lithium pyrophosphate, lithium selenate, lithium selenite, lithium tetrachloroafuminate, lithium thiomethoxide, lithium thiosulfate, lithium thiosulfide, lithium thiosulfite, lithium tri-actoxyborohydride, lithium trimethylsilonate, lithium triethylsilonate, lithium tris(1-pyrazoly)borohydride, including analogues, homologue, isomers and derivatives thereof. See Lithium Chemistry: A Theorical and Experimental Overview, Sapse, Schleyer, John Wiley & Sons, N.Y. (1995), incorporated 1 o herein by reference. Non limiting examples of the boron derivative compounds of this invention include: alkyl boron compounds, aryl boron compounds, 1,3,2-benzodioxaborole, diisopropoxymethylborane, ethylborane, diethylborane, diemthylborane, dicyclohexylborane, boric acid esters (e.g.
borate ester, dimethyl borate, di-n-butyl borate, dicyclohexyl borate, didodecylborate, di-p-cresyi borates), phenylboronic acid, 2-phenyl-1,3,2-dioxborinane, pyrrolyboranes (e.g. 1-pyrrolyborane, 2-pyrrolyborane), tetra-butylammonium borohydride, tetramethylammonium borohydride, tetraisoproplyammonium borohydride, tetrapropylammonium borohydride, tetraethylammonium borohydride, tetraisobutyiammonium borohydride, tetra-2o tert-butylammonium borohydride, tetra-sec-butylammonium borohydride, tetrabutylammonium cyanoborohydride, tetramethylammonium cyano-borohydride, tetraisoproplyammonium cyanoborohydride, tetra-propylammonium cyanoborohydride, tetraethylammonium cyanoborohydride, tetraisobutylammonium cyanoborohydride, tetra-tert-butylammonium 2 5 cyanoborohydride, tetra-sec-butyfammonium cyanoborohydride, tetramethylammonium triacetoxyborohydride, thiopheneboric acid, 2-thiopheneboric acid, 3-thiopheneboric acid, tolylboronic acid (e.g. o-tolylboronic acid, p-tolylboronic acid, m-tolylboronic acid), tributoxyborane, tributylborane, tri-sec-butylborane, tri-tert-butylborane, tributylborate, tri-tert-3o butylborate, trimethoxyboroxine, trimethylamineboran, trimethylborate, trimethylboroxine, trimethylborazine, trimethylene borate, triphenylborate, triphenylborane, tribenzyl borate, borate, trisiamylborane, tris(2-methoxyethyl)borate, boron hydride, lithium borohydride, sodium borohydride, boron hydrate, boron hydride, boron anhydride, triethylboron (C2H5)3, 35 decaborane, borazoles, aluminimum borohydride, beryllium borohydride, lithium borohydride, hexamethyldiamineborane (CH3)3NBH(CH3)3), (CH3)2B1, berylliumborohydride (Be(BH4)2), trimethoxytriborate (BO)3{OCH3)3, C4H9B{OH)2, AI(BH4)2, Be(BH4)2, LiBH4, B(OC2H5)3, B(OCH3)3, trimethoxytriborane, 3-bromophenylboronic acid, trimethoxy borate, triethoxy borate, triproxyborate, tributoxyborate, triisobutoxyborate, tri-tert-butoxyborate, tri-sec-butoxyborate, tri-phenoxyborate, tri-phenoxyboroamine, tri-phenoxyborane, phenylboronic acid, benzylboronic 5 acid, cylohexylboronic acid, cylohexenylboronic acid, cyclopentylboronic acid, methyiphenylboronic acid, methylcylohexylboronic acid, methyfcyclopentyl-boronic acid, rnethylbenzylboronic acid, dimethylphenylboronic acid, dimethylcylohexylboronic acid, dimethylcyclopentylboronic acid, dimethylbenzylboronic acid, diphenylboronic acid, dibenzylboronic acid, 10 dicylohexylboronic acid, dicylohexenylboronic acid, dicyclopentylboronic acid, methyldiphenylboronic acid, bis[(methyl)cylohexyl]boronic acid, bis[(methyl)cyclopentyl]boronic acid, bis[(methyl)benzyl]boronic acid, bis[(dimethyl)phenyl]boronic acid, bis[(dimethyl)cylohexyl]boronic acid, bis[(di-methyl)cyclopentyl]boronic acid, bis[(dimethyl)benzyl]boronic acid, 15 phenylboroncarbonyl, benzylboroncarbonyl, cylohexylboroncarbonyl, cylohexenylboroncarbonyl, cyclopentylboroncarbonyl, methylphenylboroncarbonyl, methylcyfohexylboroncarbonyl, methylcyclopentylboroncarbonyl, methylbenzylboroncarbonyl, phenylboronic acid carbonyl, benzylboronic acid carbonyl, cylohexylboronic acid carbonyl, 20 cylohexenylboronic acid carbonyl, cyclopentylboronic acid carbonyl, methylphenylboronic acid carbonyl, methylcylohexylboronic acid carbonyl, methylcyclopentylboronic acid carbonyl, methylbenzylboroncarbonyl, dimethyiphenylboroncarbonyl, dimethylcyiohexylboroncarbonyl, dimethyl-cyclopentylboroncarbonyl, dimethylbenzylboroncarbonyl, 25 diphenylboroncarbonyl, dibenzylboroncarbonyl, dicylohexylboron-carbonyl, dicylohexenylboroncarbonyl, dicyclopentylboroncarbonyl, methyldiphenylboroncarbonyl, di[(methyl)cylohexyl]boroncarbonyl, di[{methyl)cyclopentyl]boroncarbonyl, di[(methyl)benzyl]boroncarbonyl, di[(dimethyl)phenyl]boroncarbonyl, di[(dimethyl)cylohexyl]boroncarbonyl, 30 di[(dimethyl)cyclopentyl]boroncarbonyl, di[(dimethyl)benzyl]boroncarbonyl, phenylboromethoxide (phenylborodimethoxide C6H5B(OCH3)2), benzylboromethoxide, cylohexylboromethoxide, cylohexenylboromethoxide, cyclopentylboro-methoxide, methylphenylboromethoxide, methylcylohexylboro-methoxide, methylcyclopentylboromethoxide, 35 methylbenzyl-boromethoxide, methylphenylboromethoxide, dimethylphenylboromethoxide, methylcylohexylboromethoxide, dimethylcylohexylboromethoxide, methylcyclopentylboromethoxide, dimethylcyclopentylboromethoxide, methylbenzylboromethoxide, dimethylbenzylboromethoxide, diphenylboromethoxide, dibenzylboromethoxide, dicylohexylboromethoxide, dicylohexenyl-boromethoxide, dicyclopentylboromethoxide, di(methylphenyl)boromethoxide, di(methylcylohexyl)boromethoxide, di(methylcyclopentyl)boromethoxide, di(methylbenzyl)boromethoxide, di(dimethylphenyl)boromethoxide, di(dimethylcylohexyl)boromethoxide, di(dimethylcyclopentyl)boromethoxide, di(dimethylbenzyl)boromethoxide, phenylboroethoxide (phenylborodiethoxide C6H5B(OCH3)2), benzylboroethoxide, cylohexylboroethoxide, cylohexenylboroethoxide, cyclopentylboroethoxide, l0 methylphenylboroethoxide, methylcyfohexylboroethoxide, methylcyclopentylboroethoxide, methylbenzylboroethoxide, methylphenylboroethoxide, dimethyiphenylboroethoxide, methylcylohexylboroethoxide, dimethylcylohexylboroethoxide, methylcyclopentylboroethoxide, dimethylcyclopentylboroethoxide, methylbenzylboroethoxide, dimethylbenzylboroethoxide, diphenyl-boroethoxide, dibenzylboroethoxide, dicylohexylboroethoxide, dicylohexenylboroethoxide, dicyclopentylboroethoxide, di(methyl-phenyl)boroethoxide, di(methylcylohexyl}boroethoxide, di(methyl-cyclopentyl)boroethoxide, di(methylbenzyl)boroethoxide, di(di-methylphenyl)boroethoxide, di(dimethylcylohexyl)boroethoxide, di(dimethylcyclopentyl)boroethoxide, di(dimethylbenzyl)boroethoxide, phenylboric acid, benzylboric acid, cylohexylboric acid, cylohexenylboric acid, cyclopentylboric acid, methylphenylboric acid, methylcylohexylboric acid, methylcyclopentylboric acid, methylbenzylboric acid, dimethylphenylboric acid, dimethylcylohexylboric acid, dimethylcyclopentylboric acid, dimethylbenzylboric acid, dibenzylboric acid, dicylohexylboric acid, dicylo-hexenylboric acid, dicyclopentylboric acid, methyldiphenylboric acid, bis(methylcylohexyl)boric acid, bis[methylcyclopentyl]boric acid, bis[methyl-benzylJboric acid, bis[dimethylphenyl]boric acid, bis[dimethylcylohexyl]boric acid, bis[dimethylcyclopentyl]boric acid, bis[dimethylbenzyl]boric acid, aminophenylboronic acid,3-aminophenylboronic acid, diborane, tetramethoxydiborane, tetraethoxydiborane, boric acid, borazine, borocar bonate, borane-tert-butylamine, tetraethylammonium borohydride, tetraethyl-ammonium tetrafluoroborate, tetrapropylammonium tetrafluoroborate, naphthylboronic acids (e.g. 1-naphthylboronic acid, 2-naphthylboronic acid, 3-naphthylboronic acid, 4-naphthylboronic acid}, methylnaphthlboronic acid, biphenylboronic acid, carborane, cyclohexylamine diborane, methylbenzeneboric acid, dimethylbenzeneboric acids (e.g. 3,5-WO 99/66009 . PCTIUS99II3751 dimethylbenzeneboric acid), hexadecaneboronic acid, tetreadecaneboronic acide, phenylethylboroamine, methylborazine, dimethylborazine, trimethylborazine, ethylborazine, diethylborazine, triethylborazine, carboborazine, dicarboborazine, tricarboborazine, triisopropoxyboroxine, tripropoxyboroxine, trimenthyl borate, trimenthyl bovine, trimenthyl borane, trimethallyl borate, trimethallyl bovine, tripentyl borate, tripentyl bovine, tripentyl borane, trimethyl borate, trimethylborine, triethylborine, triethylborane, triethylborate, tripropylborane, tripropylborine, tripropylborate (tripropoxyborane), triisopropylborane, triisopropylborate, triisopropylborine, 1 o tri-iso-butylborane, tri-iso-butylborate, tri-sec-borane, tri-sec-borate, tri-sec-borine, tributyl borate, tributyl bovine, tributyl borane, tri-tert-butyl borate, tri-tert-butyl bovine, tri-tert-butyl borane, triphenyl borate, triphenyl borane, tricyclohexylborate, tricyclohexylborane, dimethyl boric acid, diethylboric acid, dipropylboric acid, diisopropylboric acid, di-iso-butylboric acid, di-sec-boric acid, dibutylboratic acid, di-tert-butylboric acid, diphenylboric acid, dicyclohexylboric acid, boron tribromide, sodium tetrafluoroborane, sodium trimethylborohydride, triethylborohydride, sodium tripropylborohydride, sodium triisopropylborohydride, sodium tributylborohydride, sodium triisobutyl-borohydride, sodium-tert- butylborohydride, sodium-sec-butylborohydride, 2o sodiumphenylborohydride, potassium tetrafluoroborane, potassium trimethylborohydride, triethylborohydride, potassium tripropylborohydride, potassium triisopropylborohydride, potassium tributylborohydride, potassium triisobutylborohydride, potassium-tert- butylborohydride, potassium-sec-butylborohydride, potassium phenylborohydride, butylboronic acid, sodiumborohydride, methyldichloroborane, ethyldichloroborane, propyldichloroborane, isopropyldichloroborane, butyldichloroborane, isobutyldichloroborane, tertbutyldichloroborane, secbutyldichloroborane, phenyldichloroborane, methylboric acid, ethylboric acid, trichloroborazine, borane-tetrahydrofuran, 3 o tetrafluoroboric acid, boron trichloride, tre-sec-butylborane, boran-trimethylamine, borane-triethylamine, borane-N,N-diethylaniline, boran-pyridine, borane-tert-butylamine, borane-morpholine, borane-dimethylamine, borane-diethylamine, trisiamylborane, trisiamylborate, disiamylborane, disiamylborate, trimesitylborane, sodium metaborate, lithium metaborate, potassium metaborate, sodium metaborane, borane-tributylphosphine, lanthanum hexaboride, boran-triphenylphosphine, boran-tributylphosphine, cyclopentadienylboran, methyicyclopentadienylboran, boran-N,N-diisopropylborohydride, N,N'-bis(monoisoipinocampheylborane~N,N,N'N'-tetramethylethylenediamine, boron nitride, 4-{borane-dimethylamine)benzene, 4-(borane-dimethylamine)pyridyl, 3-(methylthio)proplyborane, tris(dimethylamino)borane, butyldiisopropoxyborane, triphenyl borane sodium, sodiumtetraphenylborane, sodiumtetraphenylborane, sodium tetrakis(1-imidazolyl)borane, sodium tetrakis(1-imidazolyl)borate, diisopro-poxyphenylborate, diisopropoxymethylborate, diisopropoxyethylborate, boron-ammonia, borontrifluoride, diethyl(3-pyridyl)borane, dimethyl(3-pyridyl)borane, lithium thexylborohydride, dichloromethyldiisopropylborate, diethyl-methoxyborane, dipropylmethoxyborane, diisopropylmethoxyborane, to diethylethoxyborane, dipropylethoxyborane, diisopropylethoxyborane, boran-piperidine, diphenylborinic anhydride, tris(trimethylsilyl)borate, tris(tri-methylsilyl)borane, trimethylacetic acid with diethylboinic acid, (2-methylpropyl)borinic acid, boroglycine, boron alchols, boron etherates, boron acetates {e.g. propylborodiacetate, phenylborodiacetate, boron tris(trifluoro)-acetate), sodium tris{1-pyrazolyl)borohydride, sodium perborate, tolylboronic acid, aluminum diboride, chlorodicyclohexylborane, methyldicyclohexyl-borane, ethyldicyclohexylborane, propyldicyclohexylborane, isopropyldicyclohexylborane, dimethyicyclohexylborane, diethyl-cyclohexyfborane, dipropylcyclohexylborane, diisopropylcyclohexylborane, lithium tetramethyfboron, lithium tetraethylboron, lithium tetrapropyllboron, lithium tetraisopropylboron, tetrabutylboron, lithium tetraisobutylboron, lithium tetra-sec-butylboron, tetra-tart-butylboron, lithium tetraphenylboron, potassium hydroxide with trimethylboron, potassium hydroxide with triethylboron, potassium hydroxide with tripropyliboron, potassium hydroxide with triisopropylboron, tributylboron, potassium hydroxide with tri-isobutylboron, potassium hydroxide with tri-sec-butylboron, tri-tart-butylboron, potassium hydroxide with triphenylboron, vinylphenylboronic acid, 4-vinylphenylboronic acid, boron phosphide, boron carbide, borinoaminoborine, boroethane, pentaborane, hexaborane, decaborane, triselenideborane, 3o hexasilicide borane, trisilicide borane, trichloroborine dimethyletherate, trichloroborine trimethlyammine, trimethylborine trimethlyammine, trimethyl-borine triethlyammine, triethylborine trimethlyammine, tricyclohexylborine, tri-n-hexyltriborine trioxane, triisoamylborate, triisoamylborine, tri-p-anisylborine, trimethoxyboroxine, trimethylamminoborine, triethylamminoborine, tripropylamminoborine, triisopropylamminoborine, triisobutylamminoborine, tributylamminoborine, tri-sec-butylamminoborine, tri-tart-butylamminoborine, triphenylamminoborine, tribenzylamminoborine, trimethylamminoboric acid, triethylamminoboric acid, tripropylamminoboric acid, triisopropylamminoboric acid, triisobutylamminoboric acid, tributylamminoboric acid, tri-sec-butylam-minoboric acid, tri-tart-butylamminoboric acid, triphenylamminoboric acid, tribenzylamminoboric acid, trimethyldiborane, triethyldiborane, tripropyl-diborane, trimethyltriborinetriamine (B), triethyltriborinetriamine (B), trimethylt-riborinetriamine (N), triethyltriborinetriamine (N), trimethyltriborinetriamine (N-B-B'), triethyltriborinetriamine (N-B-B'), tri-B-naphthylborate, tri-a-naphthaborate, trlpehnylborineammine, tri-p-tolyborine, tri-p-xylxborine, including analogues, homologues, isomers and derivatives thereof.
Corresponding compounds of aluminum, gallium, indium, and thallium are to contemplated. See Organv Boron Chemistry, Volumes I & II (and subsequent volumes, editions, or supplements), Howard Steinberg, InterScience Publishers (1966), Boron-Nitrogen Gompounds, Niedenzu, Dawson, New York, Academic Press (1965), The Or4anic Compounds of Boron. Aluminum.
Gallium. Indium, and Thallium, Nesmeianov, Nikolaevich, Amterdam, North-Holland Pub. Co. (1967), Peroxides. Superperoxides. and azomides of Alkali and Alkali Earth Metals, Perekisi, N.Y., Plenum Press (19966), incorporated herein by reference.
Non-limiting examples of sodium derivative compounds of this invention include: sodium bis(dimethylsilyl~mide, sodium bis(trimethyl-2o silyl)amide, oxamic acid, P-aminosalicylic acid sodium salt, sodium salt 5-nitroorotic acid, sodium D-gluconate, sodium hexacyanoferrate(III) {Li3Fe(CN)6), sodium diphenylphosphide, sodium acetate, sodium acetate acid, sodium salt acetic acid, sodium acetamide, sodium anilide, sodium azide, ammonium diisodium amminepentacyanoferrate, sodium benzamide, sodium antimonide, sodium orthoarsenate, sodium orthoarsenite, sodium meta-arsenite, sodium diborane, sodium pentaborate, sodium dihydroxy diborane, sodium borohydride, sodium cadium iodide, sodium chloride, sodium calcium chloride, sodium carbide, sodium carbonate, sodium hydrogen carbonate, sodium alkyl carbonates, sodium aryl carbonates, sodium methyl carbonate, sodium ethyl carbonate, sodium carbonyl, sodium cobalt (II) cyanide, sodium cobalt (III) cyanide, sodium cobaltinitrite, sodium cynomanganate (II), sodium cynomanganate (lll), sodium citrate, sodium ferrosilicon, sodium ferricyanide, sodium ferrocyanide, sodium nitroferricyanide, sodium aminepentacyanide, sodium formates, sodium hydride, sodium hydroxide, sodium manganate, sodium permanganate, sodium methionate, sodium napthenate, sodium nitride, sodium nitrate, sodium nitrite, sodium nitrobenzene (e.g. sodium-p-nitrobenzene), sodium nitrophenoxide, sodium etherate, sodium chromate, sodium oleate, sodium oxalate, sodium oxalatoferrate (II), sodium oxaiatoferrate (III), sodium monoxide, sodium oxide, sodium peroxide, sodium, sodium mono-orthophosphate, sodium hypophosphite, sodium orthophosphite, sodium hydroxoplumbate, sodium rhodium cyanide, sodium selenide, sodium 5 selenite, sodium selenocynate, sodium seienocyanoplatinate, sodium disilicate, sodium metasilicate, lithium sodium carbonate, lithium sodium ferricyanide, sodium hydroxostannate, sodium disufide, sodium hydrosulfide, sodium pentasulfide, sodium tetrasulfide, sodium trisulfide, sodium telluride, sodium thioarsenate, sodium thioarsenite, sodium trithiocarbonate, sodium to thiocyanate, sodium amide, sodium salt (E,E)-2,4-hexadienoic acid, disodium fluorophosphate, disodium fluorophosphite, trisodium phosphate, trisodium phosphite, sodium perchlorate, propanoic acid sodium salt, sodium formate, sodium cyanate, sodium hexacyanocobaltate (III), sodium hypophosphite, sodium hexaflurorsilicate, sodium nitroprusside, sodium phenoxide, sodium 15 phosphate (dibasic, monobasic, tribasic), sodium salicylate, sodium selenide, sodium tetracyanonickelate (II), sodium tetrafluoroborate, sodium xanthogenate, sodium -p-aminobenzoate, sodium copper ferrocynanide, sodium cupric ferrocyanide, sodium hexafluorophosphate, sodium hexanitricobaltate lll, sodium naphthenate, sodium -B-naphthoxide, sodium 20 polysulfide, lithium -sodium phosphate, sodium stearate, sodium sulfide, sodium sulfite, sodium sulfate, sodium thiocyanate, sodium xanthate, sodium fluorosilicate, N-sodiumethylenediamine, oxalic acid disodium salt, sodium beta-hydropyruvic acid, sodium 1,1-dimethylurea, sodium 1,1-diethylurea, sodium 1,1-diepropylurea, sodium xanthate, sodium ethylxanthate, sodium 25 rnethylxanthate, sodium salt thiophenol, sodium triphenylmethylsodium, methylsodium, ethylsodium, sodiumethynyl(acetylide), propylsodium, isopropylsodium, butylsodium, isobutylsodium, secbutylsodium, tertbutylsodium, pentasodium, hexylsodium, heptasodium, amylsodium, isoamylsodium, benzylsodium, dimethylbenzyisodium, tolylsodium, 30 dodecylsodium, cyclopentadienylsodium, methylcyclopentadienylsodium, cyclohexylsodium, sodiumheptyl, sodiumdodecyl, sodium tetradecyl, sodium hexadecyl, sodium octadecyl, phenylsodium, sodium o-tolyl, sodium m-tolyl, sodium p-tolyl, sodium-p-chlorophenyl, sodium p-bromophenyl, sodium o-anisyl, sodium m-anisyl, sodium p-anisyl, sodium diethoxyphenyl, sodium 35 dimethoxyphenol, sodium m-cumyl, sodium p-ethoxyphenyl, sodium m-dimethylaminophenyl, sodium 9-flourene, sodium a-napthyl, sodium b-napthyl, sodium p-phenylphenyl, sodium 9-phenyianthryl, sodium 9-anthryl, sodium 9-methylphenanthryl, sodium pyridyl, sodium 2-pyridyl, sodium 3-pyridyl, sodium 6-bromo-2-pyridyl, sodium 5-bromo-2-pyridyl, sodium dibenzofuryl, sodium 3-quinoyl, sodium 2-lepidyl, sodium triphenylmethyl, sodium 2,4,6-trimethylphenyl, sodium 2,4,6-triisopropylphenyl, sodium 2,3,5,6-tetraisopropylphenyl, sodium tetrabutylphenyl, thiophenedisodium, toluenedisodium, diphenylethylenedisodium, sodiumamylethynyl, sodiumphenylethynyl, sodiummethoxybromophenyl, sodium phenylisopropyl, sodium tetraphenylboron, sodium tetramethylboron, sodium a-thienyl, sodium m-trifluoromethylphenyl, phenylethynylsodium, 3-furylsodium, phenylisopropylsodium, dibenzofuranylsodium, sodium dimethylbenzyl, l0 sodium selenocyanate, sodium trimethylsilanolate, diphenylphosphide, sodium benzoate, sodium tert-butyl carbonate, sodium azide, di-sodium-cyanamide, sodium cyanide, sodium dicyanamide, cyclohexanebutyric acid sodium salt, cyclohexane acid sodium salt, cyclopentadientylsodium, sodium tri-tert-butoxyaluminum hydride, sodiumaluminum-tri-tert-butoxide, sodium triethylborohydride, sodium trimethylborohydride, sodium tripropylborohydride, sodium triisopropylborohydride, sodium tributylborohydride, sodium triisobutylborohydride, sodium tri-sec-butylborohydride, sodium tri-tert-butylborohydride, sodium trisiamylborohydride, sodium chlorate, sodium tert-butoxide, sodium sec-butoxide, iso-butoxide, sodium antimonate, sodium diphenylphosphide, sodium bis(trismethylsilyl) amide, trisodium phosphate, sodium selenocyanate, sodium tri-sec-butylborohydride, sodium triethylsilano-late, sodium thiocyanate, sodium acetylide, sodium chlorate, sodium salicylate, sodium di-sodium tetracarbonylferrate, sodium tetraphenylborate, sodium triethylborohydride, sodium triacetoxyborohydride, sodium triphenylborane, sodium hydroxide, sodium diphenylphosphide, sodium methoxide, sodium ethoxide, sodium tri-sec-butylborohydride, tri-tert-butylborohydride, sodium triethylborohydride, sodium triphenylborohydride, sodium trisiamylborohydride, sodium metavanadate, sodium cyclohexane-butyrate, sodium hexachloroplatinate, sodium thiocyanate, sodium selenocyanate, sodium cyanate, sodium floride, sodium hexafluoro-antimonate, sodium hexafluoroaluminate, sodium hexafluoroarsenate, sodium hexafluorosilicate, sodium hexacyanocobalt(Il~errate(II), disodiumhexacyanocobalt(Il~errate(II), sodium hexafluorotitanate, sodium hexafluorozirconate, sodium hexahydroxyantimonate, sodium hexachlororuthenate, sodium hexachloropalladate, sodium formate, sodium tetracyanonickelate, sodium tetrafluoroaluminate, sodium tetrafluoroborate, sodium thioacetate, L-glutamic acid monosodium salt, fumaric acid sodium salt, oxamic acid sodium salt, sodium salt Biphenyl-phospane, P-aminobenzoic sodium salt, aminobenzole acid sodium salt, alpha-napthaleneacetic acid sodium salt, disodium salt 2,6-naphthaienedicarboxlic acid, sodium cyclcohexanetherate, sodium phthalimide, P-aminosalicylic acid sodium salt, sodium salt 3,5-dimethylcyclohexyl sulfate, indolebutyric acid sodium salt,indole-3-butyric acid sodium salt, diphenylphosphide, sodium dimethylsilanolate, sodium triethylborohydride, sodium propoxide, sodium isopropoxide, sodium butoxide, sodium sec-butoxide, sodium pentoxide, sodium tert-pentoxide, sodium hydrogenphthalate, sodium oxalate, sodium hydrogensulfate, monosodium acetylenedicarboxylic acid, sodium 1o pyrophosphate, sodium dihydrogenphosphate, sodium hexoate (sodium salt hexoic acid), sodium diphenylphosphide, sodium trimethylsilonalate, sodium phthalic acid, P-aminobenzoic acid sodium salt, monosodium L-aspartic acid, tetraphenyldisodium (C6H5)2CLi2C(C6H5)2, sodiumethylphenyl (LiCH2C6H5), sodium bromate, sodium hydrogenphospate, monsodium salt D-shaccharic acid, DI-asparatic sodium salt, (R)-alpha-hyroxymethylaspartic acid sodium salt, sodium fluoride, sodium iodate, sodium salt ethyl malonate, sodium thioacetate, sodium phenol, sodium salt aminobenzoic acid, sodium aminophenol salt, sodium cyclohexenol, sodium methylcyclohexenol, sodium cyclopropanol, sodium methylcyclopropanol, sodium cyclobutanol, sodium 2o methylcyclobutanol, sodium methylcyclopentanol, sodium cyclopentanol, sodium cyclohexenol, sodium methylcyclohexenol, sodium dimethylcyclohexenols (e.g. sodium 3,5-dimethylcyclohexanol, sodium 2,3-dimethylcyclohexanol, sodium 2,6-dimethylcyclohexanol, sodium 2,5-dimethylcyclohexanol, 3,5-dimethylcyclohexanol), sodium o-ethylxanthic acid, 2 5 monosodium salt 2-ketoglutaric acid, disodium salt, ketomalonic acid, sodium salt lactic acid, disodium thiosulfate, sodium antimony tartrate, sodium dichloroacetate, sodium dimethylacetate, sodium diethylacetate, sodium dipropylacetate, sodium metaborate, sodium tetraborate, sodium tetrachlorocuprate, sodium acetoacetate, sodium diisopropylamide, sodium 3o diethylamide, sodium dimethylamide, sodium bis(dimethylsilyl)amide, disodium phthalocyanine, disodiumtetrabromocuprate, disodium tetrabromonickelate, disodiumtetrachloromanganate, disodiumbutadiyne, sodium cyclopentadienide, sodium dicyclohexylamide, sodium diethylamide, sodium dimethylamide, sodium dipropylamide, sodium diisopropylamide, 35 sodium thexylborohydride, sodium tri-tert-butoxyaluminohydride, sodium trimethylsilyl)acetylide, sodium triethylsilyl}acetylide, sodium tris[(3-ethyl-pentyl~xy)aluminohydride, (phenylethynyl}sodium, 2-thienylsodium, sodium diethyldihydroaluminate, sodium dimethyldihydroaluminate, sodium aluminum hydride, sodium bifluoride, sodium biphenyl, sodium biselenite, sodium bis{2-methoxyethoxy~luminum hydride, sodium bismuthate, sodium borate, sodium chlorite, sodium cobaltnitrite, sodium cyanoborohydride, sodium cyclopentadienide, sodium dicyanamide, sodium hexametaphosphate, sodium hexanitrocofbaltate, sodium hydrogenphosphite, sodium hydrogenselenite, sodium hydrogensuifite, sodium hydrosulflte, sodium hypochloride, sodium metaarsenite, sodium metabisulfide, sodium metaperiodate, sodium methacrylate, sodium nitroferricyanide, oxybate, sodium pentamethylcyclopentadienide, sodium phenolate, polyphosphate, to sodium polyphosphite, sodium propionate, sodium pyrophosphate, sodium selenate, sodium selenite, sodium tetrachloroaluminate, sodium thiomethoxide, sodium thiosulfate, sodium thiosulfide, sodium thiosulfite, sodium triactoxyborohydride, sodium trimethylsilonate, sodium triethylsilonate, sodium tris(1-pyrazoly)borohydride, including analogues, homologues, isomers and derivatives thereof.
The non limiting examples of aluminum derivative compounds of this invention include: diisobutylaluminum hydride, dimethylaluminum hydride, dimethylaluminum hydride, dipropylaluminumhydride, diisopropylaiuminumhydride, dibutylaluminumhydride, di-tart-butylaluminum hydride, di-sec-butylaluminum hydride, diisobutylaluminum chloride, ethylaluminum sesquichloride, lithium aluminum hydride, lithium tri-tert-butoxyaluminum hydride, lithium-aluminum alloy, aluminum triethoxide, aluminum trimethoxide, aluminum tripropoxide, aluminum triisopropoxide, aluminum tri-tart-butoxide, aluminum tri-sec-butoxide (aluminum sec-butoxide), aluminum tri-isobutoxide, aluminum tributoxide, aluminum pentoxide, diethylaluminum ethoxide, aluminum phosphate, diethylaluminum chloride, diethylaluminum cyanide, diethylaluminum ethoxide, diethylaluminum methoxide, diisobutylaluminum hydride, diisobutylaluminum chloride, diisobutyalumnum fluoride, tetraisobutyldialuminoxarie, 3o triethylaluminum, trimethylaluminum, tributylaluminum, triisobutylaluminum, tri-sec-butylaluminum, tri-tart-butylaluminum, tripentaluminum, triphenylaluminum, triamylaluminum, triisoamylaluminum, tripropylaiuminum, triisopropylaluminum, triisobutylaluminum, triisobutyldialuminoxane, trioctylaluminum, sodium aluminum hydride, bis{2-methoxyethoxy}aluminum hydride, aluminum borohydride, aluminum hydride, dimethlylberyllium, potassium tri-tart-butoxyaluminum hydride, sodium tri-tart-butoxyaiuminum hydride, lithium tri-tart-butoxyaluminum hydride, aluminum sec butoxide, aluminum tart-butoxide, aluminum acetylacetone, aluminum ethoxide, aluminum methoxide, aluminum propoxide, aluminum isopropoxide, aluminum butoxide, aluminum isobutoxide, aluminum pentoxide, aluminum metaphosphate, aluminum hydroxide, aluminum metaphosphite, aluminum hydroxystearate, aluminum monostearate, aluminum nitrate, aluminum fluoride, aluminum fluoride trihydrate, sodium diethyldihydroaluminate, sodium hexafluoroaluminate, aluminum hexafluorosilicate, lithium aluminum hydride, lithium aluminum hydride bis(tetrahydrofuran), lithium tris((3-thyl-3-pentyl)oxy)aluminohydride, lithium tri-tart-aluminohydride, aluminum-nickel catalyst, aluminum silicate, aluminum silicate hydroxide, aluminum chloride 1 o hydrate, diethylaiuminum chloride, sodium bis(2-methoxyethoxy)aluminum dihydride, aluminum carbide, aluminum phosphate, aluminum acetate (aluminum diacetate hydroxide), dihydroaluminum acetate, aluminum formoacetate, lithium aluminate, aluminum salt lactic acid, tetramethyllithiumaluminum salt (LiAI(CH3}4), tetaethyllithiumaluminum salt, tetrapropyllithiumaluminurn salt, tetraisopropyllithiumaluminum salt, tetra-butyllithiumaluminum salt, tetraisobutyllithiumaluminum salt, tetra-sec-butyllithiumaluminum salt, tetra-tart-butyllithiumaluminum salt, tetraphenyilithium aluminum salt, aluminum tririconoleate, aluminum metaphosphate, sodium aluminum hydride, aluminum dodecaboride, aluminum diboride, aluminum arsenide, aluminum lactate, aluminum titanium chloride, tri(N-nitroso-N-phenylhydroxylaminoato)aluminum, aluminum acetylacetonate, methylaluminum dichloride, ethylaluminum dichloride, propylaluminum dichloride, isopropylaluminum dichloride, butylaluminum dichloride, sec-butylaluminum dichloride, tart-butylaluminum dichloride, isobutylaluminum dichloride, phenylaluminum dichloride, ethylaluminum sesquichloride, methylaluminum sesquichloride, methylaluminoxane, propylaluminum sesquichloride, ethylaiuminoxane, sodium bis(2-rnethoxyethoxy)aluminum, aluminum magnesium silicate, aluminum hydroxychloride, aluminum phosphide, aluminum potassium sulfide, 3o aluminum octoate (aluminum ethylhexonate), aluminum diformate, aluminum triformate, aluminum chromate, aluminum napthenate, aluminum oleate, aluminum palmite, aluminum pictrate, aluminum sodium silicate, aluminum sodium chloride, aluminum isopropylate, aluminum magnesium ethoxide, trimethylaluminum etherate, triethylaluminum etherate, including analogues, homologues, isomers and derivatives thereof. Corresponding compounds of gallium, indium, thallium are contemplated in the practice of this invention.
The non-limiting examples of silicon derivative compounds of this invention include: dimethoxymethylsilane, dimethoxyethylsilane, diethoxymethylsilane, dipropoxymethylsilane, diisopropoxymethylsiiane, dibutoxymethylsilane, diisobutoxyrnethylsilane, di-sec-butoxymethylsilane, di-sec-butoxyrnethylsifane, diethoxyethylsilane, dipropoxyethylsilane, diisoprop-oxyethylsilane, dibutoxyethylsilane, diisobutoxyethylsilane, di-sec-butoxyethyl-5 silane, di-sec-butoxyethylsilane, diethoxydimethylsilane, dimethoxydi-methylsilane, dipropoxydimethylsilane, diisopropoxydimethylsilane, dibutoxydimethylsilane, diisobutoxydimethylsilane, di-sec-butoxydi-methylsilane, di-sec-butoxydimethylsilane, diethoxymethylethylsilane, ethoxytrimethylsilane, ethoxytriethylsilane, ethoxytripropylsilane, 1 o ethoxytriispropylsilane, methoxytrimethylsilane, propoxytrimethylsilane, iso-propoxytrimethylsilane, butoxytrimethylsilane, isobutoxytrimethylsilane, sec-butoxytrimethylsilane, sec-butoxytrimethylsilane, phenoxytrimethylsilane, ethoxydiethylsilane, isobutyldiethoxysilane, sec-butyldiethoxysilane, butyl diethoxysilane, tertbutyldiethoxysilane, pentyldiethoxysilane, isobutyl-15 dimethoxysilane, secbutyldimethoxysilane, butyldimethoxysilane, tertbutyltri-methoxysilane, methyltrimethoxysilane, methyltriethoxysilane, pentyldimethoxysilane, diethylsilandiol, tripropylsilandiol, triisopropylsilandiol, tertbutyldimethylsilane, diethylsilanediol (C2H5Si(OH)2), methyl-tripropoxysilane, methyl-tris(dimethylsiloxy)silane, 1,1-20 diphenylsilacyclohexane, pentamethylsilanime, 1,1,1-trimethyl-N-phenyl-N-silanamine, hexamethyldisilazane, [1,1'-biphenyl]-4-yltrichlorosilane, (bromo-methyl)chlorodimethylsilane, bromomethyltrimethylsilane, (4-bromophenoxy}trimethylsilane, butylchlorodimethylsilane, trichlorobutylsilane, trimethylbutylsilane, chloro(chloromethylklimethylsilane, 25 chloro(dichloromethyl)dimethylsilane, chlorodimethylphenylsilane, chlorodimethyl-2-propenylsilane, chloroethenyldimethyisilane, chloromethylsilane, (chloromethyl)dimethylphenylsilane, chlorome-thyldiphenylsiiane, chloromethylphenylsilane, (chloromethyl~rimethylsllane, (4-chloropehoxy}trimethylsilane, phenylchlorosilane, (3-30 chlorophenyl}trimethylsilane, (3-chloropropyl~rimethylsilane, chlorotriethoxysilane, chlorotriethylsilane, trimethylchlorosilane, dichloro(chloromethyl)methylsilane, dichloro(dichioromethyl)methylsilane, dichlorodiethoxysiiane, dichlorodiethylsilane, dichlorodimethylsilane, dichlorodiphenylsilane, dichloroethenylmethylsilane, 35 methylethyldichlorosilane, dichloromethylsiiane, dichloromethyl(1-methylethyl)silane, dichloromethyl{4-methylphenyl)silane, dichloromethylphenylsilane, dichloromethyl-2-propenylsilane,dichlorophenylsilane, diethenyldiphenylsilane, diethoxydimethylsilane, diphenyldiethoxysilane, diethoxymethylphenylsilane, diethyloxymethyl-2-propenylsiiane, diethylsilane, diethyldifluorosilane, difluorodiphenylsilane, dimethyoxydimethylsilane, dimethoxydiphenylsilane, dimethylsilane, dimethyldiphenoxysilane, dimethyldiphenylsilane, dimethyl-2-propenylsilane, dimethylphenylsilane, dimethyl-diacetatesilane, diphenylsilane, 1,2,-ethenediylbis[trimethyl-(E)]silane (C8H20Si2), ethenyldiethoxymethylsilane, ethenylethoxydimethylsilane, ethenyl-triethoxysilane, ethenyltrimethylsilane, ethenyltris(1-methylethoxyrsilane, ethenyitris(2-propenyloxy)silane, ethoxytriethytsilane, ethoxytrifluorosilane, ethoxytrimethylsilane, ethoxytriphenylsilane, ethyltrifluorosilane, ethyltrimethoxysilane, 1,2,-ethynediylbis[trimethyl]silane, ethynylsilane, methoxysilane, methylsilane, methyldiphenylsilane, methylenebissilane, methylenebis[trichloro]silane, (2-methylphenoxy)triphenylsilane, methyl-phenylsilane, methyltriphenoxysilane, methyltriphenylsilane, methyltri-p-toly-silane, phenylsilane, [1,3-phenylenebis(oxy)]bis[trimethyl]silane, phenyltripropylsilane, tetraethenylsilane; tetraethylsilane, tetraethoxysilane, tetramethylsilane, tetramethoxysilane, tetrapropylsilane, tetrapropoxysilane, tetraisopropylsilane, tetraisopropoxysilane, tetrabutylsilane, tetrabutoxysilane, tetra-sec-butylsilane, tetra-sec-butoxysilane, tetra-tert-butylsilane, tetra-tert-butoxysilane, tert-iso-butylsilane, tetra-iso-butoxysilane, tetraphenylsilane, tetraphenoxysilane, triethylsilane, triethoxysilane, trimethylsilane, trimethoxysilane, tripropylsilane, tripropoxysilane, triisopropylsilane, triiso-propoxysilane, tributylsilane, tributoxysilane, tri-sec-butylsilane, tri-sec-butoxysilane, tri-tert-butylsilane, tri-tert-butoxysiiane, tert-iso-butylsilane, tri-iso-butoxysilane, triphenylsilane, triphenoxysilane, triethylmethylsilane, triethoxymethylsilane, trimethoxymethylsilane, tripropylmethylsilane, tripro-poxymethylsilane, triisopropylmethylsilane, triisoproxymethylsilane, tributylmethylsilane, tributoxymethylsilane, tri-sec-butylmethylsiiane, tri-sec-butoxymethylsilane, tri-tert-butylmethylsilane, tri-tert-butoxymethylsilane, tert-iso-butylmethylsilane, tri-iso-butoxymethylsilane, triphenylmethylsilane, triphenoxymethylsilane, diethylsilane, diethoxysilane, dimethylsilane, dimethoxysilane, dipropylsilane, dipropoxysilane, diisopropylsilane, diisopropoxysilane, dibutylsilane, dibutoxysilane, di-sec-butylsilane, di-sec-butoxysilane, di-tert-butyisilane, di-tert-butoxysilane, tert-iso-butylsilane, di-iso-butoxysilane, diphenylsiiane, diphenoxysilane, ethylsilane, ethoxysilane, rnethylsilane, methoxysilane, propylsilane, propoxysilane, isopropylsilane, isoproxysilane, butylsilane, butoxysilane, sec-butylsilane, sec-butoxysilane, tert-butylsilane, tert-butoxysilane, iso-butylsilane, iso-butoxysilane, phenylsilane, phenoxysilane, tribromomethylsilane, tributylsilane, tributylphenylsilane, trichloro(chloromethyl)silane, trichloro(4-chlorophenyl)silane, trichloro(3-chforopropyl)silane, trichloro(di-chloromethyl)silane, trichlorododecylsilane, trichloroethenylsilane, trichloroethoxysilane, trichloroethylsilane, trichlorohexylsilane, trichloromethy-Isilane, trichloro(1-methylethyl}silane, trichloro(2-methylphenyl)silane, trichloro(3-methylphenyl)silane, trichloro(2-methylpropyl)silane, trichlorootadectylsilane, trichlorooctylsilane, trichloropentylsilane, trichlorophenylsilane, trichloro(2-phenylethyl)silane, trichloro-2-propenylsilane, l0 trichloropropylsilane, triethoxysilane, triethoxyethylsilane, triethoxyethylsilane, triethoxyphenylsilane, triethoxypentylsilane, triethoxy-2-propenylsilane, triethylsilane, triethylfluorosilane, triethylphenylsilane, trifluorophenylsilane, trimethoxymethylsilane, trimethoxyethylsilane, trimethoxypropylsilane, trimethoxyisopropylsilane, trimethoxybutylsilane, trimetho-xyisobutylsilane,trimethoxy-sec-butylsilane, trimethoxy-tert-butylsilane, trimethoxyphenylsilane, trimethylsilane, trimethyl(4-methylphenyl}silane, tri-methyl(2-methylpropyl)silane, trimethylphenoxysilane, trimethylphenylsilane, trimethyl(phenyimethyl)silane, trimethyl(cyclohexylmethyl)silane, trimethyl-2-propenylsilane, trimethylpropylsilane, trimethyl[4-[(trimethylsifyl)oxy]phenyl]silane, ethenyl-triacetatesilanetriol, methyl-triacetatesilantriol, tripropylsilane, ethyldimethylsilanol, methyldiphenylsilanol, triethylsilanol, triphenylsilanol, tetrabutyl ester silicic acid (C16H3604Si), tetraethyl ester silicic acid, tetrakis(2-ethylbutyl) ester silicic acid, methylsilicate (C4H12Si04), tetraphenyl ester silicic acid, tetrapropyl ester 2 5 silicic acid, triethyl phenyl ester silicic acid, 1,2-dichloro-1,1,2,2-tetramethyldisilane, 1,2,-difluorotetramethyldisiiane, hexamethyldisiiane, 1,3-diethenyl-1,1,3,3-tetramethyfdisiloxane, 1,3-diethenyl-1,1,3,3-tetramethyldisilazane, bis(methoxydimethylsilyl)oxide, 1,1,1,3,3,3-hexaethyldisiloxane, 1,1,1,3,3,3=hexaethyldisilazane, hexamethyldisiloxane, 3 o hexamethyldisilazane, 1,1,3,3-tetramethyldisiloxane, 1,1,3,3-tetramethyl-disilazane, 1,1,3,3-tetramethyl-1,3-diphenyldisiloxane, 1,1,3,3-tetramethyl-1,3-diphenyldisilazane, 1,1,1-trimethyl-3,3,3-triphenyldisiloxane, 1,1,1-trimethyl-3,3,3-triphenyldisilazxane, docosamethyfdecasiloxane, docosamethyldecasilazane, ethenylheptamethylcyctetrasiloxane, 35 ethenylheptamethylcyctetrasilazane, heptamethylcyclotetrasiloxane, heptamethylcyclotetrasilazane, octaphenylcyclotetrasiloxane, butylmethyl(cyclic tetramer)siloxane, 2,4,6,8-tetraethenyl-2,4,6,8-tetramethylcyclotetrasiloxane (C12H2404Si4), 2,4,6,8-tetraethyl-2,4,6,8-cyclotetrasiloxane, 2,4,6,8-tetraethyl-2,4,6,8-cyclotetrasilazane, 2,4,6,8-tetra-ethyl-2,4,6,8-cyclotetrasiloxane, 2,4,6,8-tetramethylcyclotetrasiloxane, 2,4,6,8-tetramethylcyclotetrasilazane, 2,4,6,8-tetramethyl-2,4,6,8-tetraphenylcyclotetrasiloxane, 2,2,4,4,6,6-hexamethylcyclotrisilazane, hexamethylcyclotrisiloxane, 2,4,6-triethyl-2,4,6-trimethylcyclotrisiioxane, 2,4,6-methyl-2,4,6-trimethylcyclotrisiloxane, 2,4,6-methyl-2,4,6-triphenylcyclotrisiloxane, 2,4,6-mmethyl-2,4,6-tripehnylcyclotrisiloxane, decamethylcyclopentasiloxane, decamethylcyciopentasilazane, 2,4,6,8,10-pentamethylcyclopentasiloxane, 2,4,6,8,10-pentamethylcyclopentasilazane, l0 octademethylcyclononasiloxane, octademethyicyclononasilazane, hexadecamethylcyclooctasiloxane, hexadecamethylcyclooctasilazane, dodecamethylcyclohexasiloxane, dodecamethylcyclohexasilazane, hexamethylcyclohexasiloxane, tetradecamethylcycloheptasiloxane, tetra-decamethylcycloheptasilazane, decamethyltetrasiloxane, 1,1,1,3,5,7,7,7-octamethyltetrasiloxane, aminotrisilane, benzyltriethoxysilane, butyltrifluorosilane, carboxyethyldimethylsilane, chloromethylsilicane, chlorotriisocyanatesilane, dichloromethylsilicane, diethoxydibutoxysilane, diethylanilinefluorosilicate, diethyldichlorosilane, [2-(cyclohexenyl)ethyl]tri-ethoxysilane, [2-(cyclohexenyl)ethyl]methyldiethoxysilane, [2-(cyclohexenyl)ethyl]dimethylethoxysilane, [2-(cyclohexenyl~
ethyl]trimethylsilane, [2-(cyclohexenyl)ethyl]triethylsilane, cyclohexyldimethoxymethylsilane, cyclohexylmethoxydimethylsilane, cyclohexyltrimethylsilane, cyclohexyltriethylsiiane, dicyclohexyldimethylsilane, cyclohexyldimethylsilane, cyclohex-1-enyl-trimethylsilane, benzyltrimethylsilane, (1-cyclohexen-1-ylethynyl)trimethylsilane, 1-cyclohexenyltrimethylsilane, cyclohexenyloxytrimethylsilane, cyclohexyltrichlorosilane, 1-cyclopropyl-1-(trimethylsilyloxy}ethylene, phenyldimethylsilanol, phenylsilandiol, cyclohexylsilandiol, cyclohexylethylsilandiol, tert-butylsilandiol, cyclohexyldimethylsilanol, 3 o cyclohexyldiethylsilanol, benzyltrimethylsilane, N-benzyltrimethylsilylamine, phenyl dimethylsilanol, phenyl diethylsilanoi, cyclohexylethylenetrimethylsiiane, N-cyclohexylethylenetrimethylsilyiamine, cycloethylenetrimethylsilane, diphenyldiethoxysilane, diphenyldimethoxysilane, diphenyl-methyl-ethoxysiiane, diphenylmethylsilane, diphenylmethylsilandiol, diphenylsilandiol, methyl-phenyl-diethoxysilane, methyl-phenyl-dimethoxysilane, methyl-phenyl-dichiorosiiane, octadecyltri-methoxysilane, octyltriethoxysilane, octyltrimethoxysilane, 1,3-bis(3-aminopropyl}-1,1,3,3-tetramethyldisiloxane, 1,3-bis{3-aminopropyl)-1,1,3,3-tetramethyldisilazane, tertbutyldimethylsilandiol, hydroxymethylenetrimethylsilane (CH3)3CH24H), hydro-xyethylenetrimethylsilane, hydroxymethyltriethylsilane, hydrox~
ethyltriethylsilane,diethylsilanediol, dimethylsilanediol, dipropylsilanediol, diisopropylsilanediol, dibutylsflanediol, di-tert-butylsilanediol, di-iso-butylsilanediol, di-sec-butylsilanediol, diphenylsilanediol, dicyclohexyfsilanediol, cyclohexylmethylsilanediol, cyclohexylethylsilanediol, dimethoxydichforosilane, dimethylanilineflourosilicate, dimethyldi(B-chloroethoxy)silane, dimethylflourochiorosilane, dimethylsilicane, di-a-1o napthylamineflourosilicate, di-b-napthylamineflourosilicate, di-m-nitranilineflourosilicate, dinitrosodiphenylamine, diphenylar-sinophenylenetriethylsilane, diphenyldichlorophenoxysilane, di-o-toluidinefluorosilicate, di-m-toluidinefluorosilicate, di-p-toluidinefluorosilicate, docosamethyldecasiloxane, dodecamethylcyclohexasiloxane, dodecamethyl-pentasiloxane, eicosamethylnonasiloxane, silanesifanesilane-docosamethyldecasifazane, dodecamethylcyclohexasilazane, dodecamethylpentasilazane, eicosamethylnonasilazane, ethyl-diethoxyacetoxysilane, ethyldiethoxychlorosilane, ethylisocyanatesilane, ethyltriethoxysilane, ethyltriphenylsilicane, hexadacamethylcyclooctasiloxane, 2 o hexadacamethylcyclooctasiiazane, hexamethylsilicane (hexamethyldisilane), hexamethylmethylenedislane, hydroxyrnethyltrimethylsilane, methylsilicane, methyltriphenylsilicane, octadecamethylcotasiloxane, octamethyl-cyclotetrasiloxane, octamethyltrisiloxane, octadecamethylcotasilazane, octamethylcyclotetrasilazane, octamethyltrisilazane, tetraphenylenesilane, 2 5 phenylenediamineflourosilicate, phenylisocyanatesifane, phenyltrichlorosilicane, silicobenzoic acid, tetra-m-aminophenylsilane, tetrabenzylsilicane, tetra-p-biphenylylsilane, tetradecamethylcyclohep-tasiloxane, tetradecamethylcycloheptasilazane, tetradecamethylhexasiloxane, tetradecamethylhexasilazane, tetraethylsilane, tetraethylthiosilane, 30 tetrahexyfoxysilane, tetraisopropylmercaptane silicon, tetramethoxysifane, tetramethylmercaptanesilicon, tetramethylsilane, tetraphenoxysifane, tetraphenylsilane, tertapropoxysilane, tetratriethylsiloxysilane, thioisocyanatotriethylsilane, tolidinefluorosilicate(o), tri-p-Biphenylylphenyl-silane, trichloromethyltriethoxysifane, triethylbromosilane, triethylchlorosilane, 35 triethylfluorosilane, triethylphenylsilane, trimethylchloromethylsilane, trimethylethoxysilane, triphenylacetoxysifane, vinyltriphenoxysilane, vinyltriethoxysilane, silicane cyanate, dibromosilane, dibromodichlorosilane, dichlorosilane, dichlorodifluorosifane, hexaoxocyclosilane, hexacycl~ilazane, monooiodosilane, (tri-)nitrilostlane (silicylamine), trichlorosilane, trifluorosilane, siticane diimide (Si(NH)2), silicane tetramide, silicane isocyanate, silicon tetracetate, tetrabromosilane, silicon hex(di-)bromide, silcon carbide, tertachlorosilane, hexachlorodisilane, tetrafluorosilane, hexa-fluorodisilane, 5 silicon hydride (SiH4), disilane (Si2H6), trisilanepropane, tetrasilane butane, silicon nitride, silicon thiocyanate, disilicic acid, silicon cyanate, allyl-chlorodimethylsilane, allylchloromethyldimethylsitane, allyl-dichtorodimethylsilane, altyl(diisoproprylamino)dimethylsilane, allyloxy-tert-butyldimethylsilane, allytoxy-sec-butyldimethylsilane, allyfoxy-iso-butyl-1 o dimethylsilane, allylchlorodiethytsilane, allylchloromethyldiethylsilane, allyldichlorodiethylsilane, allyl(diisoproprylamino)diethylsilane, allyloxy-tert-butyldiethylsilane, allyloxy-sec-butykiiethylsilane, allyloxy-iso-butyldiethyl-silane, allyloxybutyldimethylsilane, allyloxytrimethylsilane, allyloxy triethylsilane, diallyloxydimethylsilane, triallyloxymethylsilane, 15 diallyloxydiethylsilane, triallyloxyethylsilane, diallyloxydimethoxylsilane, trtal-lyloxymethoxylsilane, diallyloxydiethoxylsilane, trialtyloxyethoxylsilane, allyltri-chlorosilane, allyltriethoxysilane, allyltriisopropylsilane, allyltripropylsilane, al-lyltriisopropyloxysilane, allyltripropyloxysilane, atlyltrimethoxysilane, allyltri-methylsilane, allyltriethylsilane, allyltriphenylsilane, 3-aminopropyltriethoxy 2 o silane, 3-aminopropyltrimethoxysilane, 3-aminoethyltriethoxysilane, 3-aminoethyltrimethoxysilane, 3-aminomethyltriethoxysilane, 3-aminomethyltri-methoxysilane, 3-aminotrimethoxysilane, 3-aminotriethoxysilane, 3-amino(cyclohexyl)propyltriethoxysitane, 3-amino(cyclohexyt)pro-pyltrimethoxysilane, 3-amino(cyclohexyl)ethyltriethoxysilane, 3-25 amino(cyclohexyl)ethyltrimethoxysilane, 3-amino(cyclohexyl)methyltriethoxysilane, 3-amino(cyclohexyl}-methyltrimethoxysilane, 3-amino(cyclohexyl)trimethoxysilane, 3-amino(cylcohexyl)triethoxysilane, trimethoxypropylsilane, trte-thoxypropylsilane, trimethoxysitane, 3-amtnopropyltrimethoxysilane, N-[3-3 o (trimethoxysilyl)propyl]aniline, N-[3-(triethoxysityl)propyl]aniline, N-[3-(triethoxysilyl)ethyt]aniline, N'-[3-(trimethoxysilyl)propyl]diethylenetriamine, N-[3-(trimethoxysilyl)propyl]ethylenediamine, N-[3-(triethoxysilyl)propyl]ethyl-enediamine, 3-(trimethoxysilyl)propyl methacrylate, 3-(triethoxysilyl)propyl methacrylate, aminotriphenylsilane, azidotrimethylsifane, azidotriethylsilane, 35 azidotripropylsilane, azidotributylsilane, azidotrimethoxysilane, azidotriethoxysilane, azidotripropoxysitane, azidotributoxysilane, bis[3-(trimethoxysilyl)propyl]amine, N,O-bis(trimethylsilyl)acetamide, bis(trimethyl-silyl)acetylene, bis(trimethylsilylkyclopentadiene, 1,4-bis(trimethylsilyl)benzene, N,O-bis(trimethylsilyl)hydroxylamine, bis(trimethylsilyl)methane, 2,3-bis(trimethylsilyloxyr1,3-butadiene, 1,2-bis(trimethylsilyloxy)cyclobutene, 1,2-bis(trimethylsilyl)cyclobutene, 1,2,3-bis(trimethylsilyl)cyclobutene, 1,2,3,4-bis(trimethylsilyl)cyclobutene, bis(trimethylsilyl)cyclobutene, 1,2-bis(trimethylsilyloxy)ethane, 2,3-bis(tri-methylsilyl~1-propene, 2,4-bis(trimethylsilyloxy)pyrimidine, 1,3-bis(trimethylsilyl)urea, O,O'-bis(trimethyisilyl)uracil, bis(trimethylsilyl)trifluoroacetamide, (1-cyclohexenyl-1-ethynyl)trimethylsilane, 1-cyclohexenyloxytrimethylsilane, 1-cyclohexyltrimethylsilane, to cyclohexyldimethoxysilane, cyclohexyftrimethoxysilane, cyclohexyldiethoxysilane, cyclohexyltriethoxysilane, cyclohexyldimethoxymethylsilane, cyclohexyltrimethoxysilane, cyclohexyldiethoxymethylsifane, cyclohexyltriethoxysiiane, cyclohexyldimethoxysilandiol, cyclohexyldiethoxysilandiol, cyclohexyldipropxymethylsilane, cyclohexyldipropxymethylsilandiol, cyclohexyltrichlorosilane, [(1-cyciopropyletheneyl)oxy]trimethylsilane, diallyldimethylsilane, diethoxymethylphenylsilane, 3-(diethoxymethylsilyl)propyiamine, diethoxymethylsilane, dimethyloctadecyline, ethyltriacetoxysilane, 2 o methyltriacetoxysilane, propyltriacetoxysilane, isopropyltriacetoxysilane, butyltriacetoxysilane, isobutyltriacetoxysilane, sec-butyltriacetoxysilane, tert-butyltriacetoxysilane, benzyltriacetoxysilane, phenyltriacetoxysilane, cycl-pentadienyltriacetoxysilane, cyclohexyltriacetoxysilane, isopropoxytrimethylsilane, isopropylaminotrimethylsilane, lithium bis(trimethylsilyl)arnide, methoxydimethyloctylsilane, methylbis(trimethylsilyloxy)vinylsilane, octyltriethoxysilane, octyltrimethoxysilane, (phenylthiomethyl)trimethylsilane, phenyltriethoxysilane, phenyl-trimethoxysilane, poly(dimethylsiloxane) silicon hexaboride, silicon nitride, 3o silicon tetracetate, silicon tetrachloride, silicon tetrafluoride, sodium bis(trimethylsilyl)amide, -tetrakis(trimethylsilyl)silane, tetravinylsilane, trichloro-3-chloropropylsilane, trichlorocyclopentysilane, cyclohexyltrichlorosilane, trichlorovinylsilane, 3-(triethoxysilyl~ropionitrile, 3-(tri-methoxysilyl)propylamine, 3-(trimethoxysilyl)propyl isocyanate, 3-(trimethoxysilyl)propyl thiocyanate, trihexylsilane, triisopropylsilane, (triisopropylsilyl)acetylene (chforotriisopropylsilane), triisopropylsilylchloride, 1-(triisopropylsilyl)pyrrole, trimethylsilylacetate, (trimethylsilyl)acetic acid, (trimethylsilyl)acetylene, trimethylsilyl cyanide, (trimethylsilylkliazomethane, b-(trimethylsilyl)-1,3-cyclopentadiene, 1-(trimethylsilyl)imidazole, 1-(trimethy-Isilyl)pyrrolidine, triphenylsilane, 1,1,1-triphenylsilylamine, triphenylsilylchloride, tris(2-methoxyethoxy~inylsilane, 2,5,5-tris(trimethylsilyl~
1,3-cylcopentadiene, tris(trimethylsilyf)borate, tris(trimethylsilyl)amine, tris(tri-methylsilyl)germaniumhydride, tris{trimethylsilyl)methane, tris(trimethylsilylmethyl)borane, tris(trimethylsilyloxy)silane, vinyltrimethoxysilane, vinyltrimethylsilane, trimethylsilyl N-(trimethylsilyl)-car bamate, triphenylsilylamine, triethoxysilylamine, tributoxysilyamine, tripropoxysilylamine, vinyltrichlorosilane, vinyltriethoxysilane, vinyl-1 o triisopropoxsilane, vinyltrimethoxysifane, vinyltriethoxysilane, dimethoxymethylvinylsilane, diethoxymethylvinylsilane, dimethoxyethylvinylsilane, diethoxyethylvinylsilane, dimethylmethoxyvinylsilane, dimethylethoxyvinylsilane, di-methylpropoxyvinylsilane, dimethylisopropoxyvinyfsilane, diethylmethoxyvinylsilane, diethylethoxyvinylsilane, diethylpropoxyvinylsiiane, diethyiisopropoxyvinylsilane, dirnethylethoxy(methylvinyl)silane, dimethoxymethyl(ethylvinyl)silane, diethoxymethyl(propylvinyl)silane, vinyltrimethylsiiane, vinyltriethylsiiane, vinyltriphenylsilane, vinyltris(2-butyiidenaminooxy)silane, vinyltris(2-methoxyethoxy)silane, vinyltris{2-methyl-2 0 ethoxy)silane, vinyltris(2-ethoxy)silane, vinyltris(trimethylsiloxy)silane, 3-(2-aminoethylamino)propyltrimethoxysilane, 3-arninopropyl-methyl-diethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminomethyltriethoxysifane, 3-aminoethyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminomethyltrimethoxysilane, 3-aminoethyltrimethoxysilane, (3-aminopropyl)tris[2-(2-methoxyethoxy)ethoxysilane, amyltriethoxysilane, 1,3-bis{chloromethyl~
1,1,3,3-tetramethyldisilazane, 1,3-bis(chloromethyl)-1,1,3,3-tetramethyldisiloxane, 1,2-bis(chlorodimethylsilyl)ethane, 1,3-bis(3-cyanopropyl}tetramethyldisiioxane, 1,3-bis(3-cyano-3o propyl)tetramethyldisilazane, bis(diethylamino)dimethylsilane, bis(dimethylaminoklimethylsilane, bis( diethylamino)diethylsilane, bis(dimethylamino)diethylsilane, 1,2-bis[(dimethylamino)dimethylsilyl]ethane, 1,2-bis(dimethylsilyl}benzene, 1,2-bis(dimethylsilyl)cyclohexene, 1,4-bis(dimethylsilyl)benzene, 1,4-bis(dimethylsilyl)cyclohexene, 1,3-bis(4-3 5 hydroxybutyl)-1,1,3,3-tetramethyldisiloxane, 1,3-bis(4-hydroxybutyl)-1,1,3,3-tetramethyldisilazane, bis(N-methylbenzamido)methylethoxysilane, 1,4-bis(trirnethylsilyl)butadiyne, N,O-bis(trimethylsilyl)acetimide, N,N-bis(tri-rnethylsilyl)methylamine, N,N-bis(trimethylsilyl}amine, N,N-bis(tri-ethylsilyl)amine, N,N'-bis(trimethylsilyl)urea, bis(trimethylsilyl)phosphite, N,O-bis(trimethylsilyl)trifluoroacetirnide, tert-butyldimethylsilane, tert-butyldimethylsilanol, (tert-butyldimethsilyl)acetylene, tert-butyldimethylsilyl cyanide, N-(tert-butyldimethylsilyl)dimethylamine, butyldimethylchlorosilane, tert-butyldimethylchlorosilane, O-(tert-butyldimethylsilyl)hydroxylamine, 1-(tert-butyldimethylsilyl)imidazole, tert-butyldiphenylsilyl cyanide, tert-butyldicyclohexylsilyl cyanide, N-tert-butyltrimethylsilylamine, tert-butyl-trimethylsilyi peroxide, tert-butyl-trimethylsilyl acetate, [2-(cyclohexenyl)ethyl]triethoxysilane, N,N-diethyltrimethylsilylamine, N,N-to diethyltriethylsilylamine, N,N-diethyl(trimethylsilylmethyl}amine, diethyl trimethylsilyl phosphite, diphenylmethylsilane, dicyclohexylmethylsilane, diphenylethylsilane, dicyclohexylethylsilane, diphenylsilane, dicyclohexylsilane, dicyclohexylsiladiol, 1,3-diphenyl-1,1,3,3-tertamethyldisilazane, 1,3-diphenyl-1,1,3,3-tertamethyldisiloxane, 1,3-dicyclohexyl-1,1,3,3-tertamethyldisilazane, 1,3-dicyclohexyl-1,1,3,3-tertamethyldisiloxane, 1,3-divinyl-1,1,3,3-tetramethyldisilazane, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, dodecyltriethoxysiiane, 1,1,3,3,5,5-hexamethyltrisilazane, 1,1,3,3,5,5-hexamethyltrisiloxane, methyl-triethoxysilane, ethyltriethoxysilane, propyltriethoxysilane, 2 0 isopropyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, isobutyltriethoxysilane, sec-butyltriethoxysilane, tert-butyltriethoxysilane, hexyltriethoxysilane, (3-isocyanatropropyl)triethoxysilane, (isopropenyloxy)trimethylsilane, isopropyldimethylchlorosilane, lithium bis(trimethylsilyl)amide, potassium bis(trimethylsilyl)amide, (3-men;,ap-topropyl)methyldimethoxysilane, (3-mercaptopropyl)triethoxysilane, (3 mercaptopropyl)trimethoxysilane, (methoxymethyl)trimethylsilane, methoxytrimethylsilane, ethoxytrimethylsilane, [3-(methylamino}propyl]trimethoxysilane, methyldiethoxysilane, 2-methylbenzosilylazole, methyl-octadecyl-dichlorosilane, methyl-octyldimethoxysilane, methyl-octyldichlorositane, methyl-phenyl-chlorosilane, methyl-phenyl-dichlorosilane, methyl-phenyl-diethoxysilane, methyl-phenyl-dimethoxysilane, (methylthio)trimethylsilane, methyltriactoxysilane, methyltri-chforosilane, ethyltrichlorosilane, methylethoxysilane, ethylethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, N-methyl-N-trimethylsilylacetamide, methylvinyldiethoxysilane, phenyltriethoxysilane, cyclohexyltriethoxysilane, Phenyltrimethoxysilane, cyclohexyltrimethoxysilane, Phenyl(methylene)triethoxysilane, cyclohexyl(methylene)triethoxysilane, pheny!(methylene)trimethoxysilane, cyclohexyl(methylene)trimethoxysilane, Phenyl(ethylene)triethoxysilane, cyclohexyl(ethylene)triethoxysilane, phenyl{ethylene)trimethoxysilane, cyclohexyl(ethylene)trimethoxysilane, phenyltrimethylsilane, phenyltriethylsilane, phenyltripropylsiiane, phenyltriisopropylsilane, phenyltributylsilane, phenyltri-sec-butylsilane, phenyltri-tert-butylsilane, phenyltriisobutylsilane, cyclohexyltrimethylsilane, cyclohexyitriethylsilane, cyclohexyltripropylsilane, cyclohexyltriisopropylsilane, cyclohexyltributylsilane, cyclohexyltri-sec-butylsilane, cyclohexyltri-tert-butylsilane, cyclohexyltriisobutylsilane, Phenyltriethoxysilanediol, cyclohexyltriethoxysilanediol, Phenyl-1o trimethoxysilanediol, cyclohexyltrimethoxysilanediol, phenyltrimethylsilanediol, phenyltriethylsilanediol, phenyltripropylsilanediol, phenyltriisopropylsilanediol, phenyltributylsilanediol, phenyltri-sec-butylsilanediol, phenyltri-tert-butylsilanediol, phenyltriisobutylsilanediol, cyclohexyltrimethylsilanediol, cyclohexyltriethylsilanediol, cyclohexyltripropy~
silanediol, cyclohexyltriisopropylsilanediol, cyclohexyltributylsilanediol, cyclohexyltri-sec-butylsilanediol, cyclohexyltri-tert-butylsilanediol, cyclohexyltriisobutylsilanediol, propyltrimethoxysilane, tetramethylsilane, 2,4,fi,8-tetramethylcyclotetrasilazane, 1,1,3,3-tetramethyldisilazane, 1,1,3,3-tetramethyldisiloxane, tetramethyltetrasilylfulvalene, trimethylethoxysilane, 2o N-(trimethylsilyl)acetamide, trimethylphenoxylsilane, 1-(trimethy-Isiloxy)cyciopentene, 1-(trimethylsiloxy)cyclohexene.
trimethoxylphenylsilane, 1-(trimethoxylsilylxyclopentene, 1-(trimethoxylsilyl)cyclohexene, triethoxylphenylsilane, 1-(tri-ethoxylsilyl)cyclopentene, 1-(triethoxylsilyl)cyclohexene, 2 5 trimethoxylcyclohexylsilane, (trimethoxylsilyl)cyclopentane, (trimethoxylsilyl)cyclohexane, triethoxylcyclohexylsilane, (triethoxylsilylkyclopentane, (triethoxylsilylkyclohexane, trimethylsilyl azide, triethylsilyl azide, tripropylsilyl azide, triisopropylsilyl azide, tributyl azide, triisobutyl azide, tri-tert-butyl azide, tri-sec-butyl azide, triphenyl 30 azide, trimethoxylsilyl azide, triethoxylsilyl azide, tripropoxylsilyl azide, triisopropoxylsilyl azide, tributoxyl azide, triisobutoxyl azide, tri-tert-butoxyl azide, tri-sec-butoxyl azide, (trimethylsiiyl)cyclopentadiene, trimethylsilyl cyanide, (trimethylsilyl)acetontrile, 35 traps-3-(trimethylsilyl)allyl alcohol, 2-{trimethylsilyl)methanol, 2-(triethylsilyl)ethanol, (trimethylsilyl)methanol, (triethylsilyl)ethanol, triisobutyl-silane, 2-(trimethylsilyl)methanol, 2-{trimethytsilyl)ethanol, O-{trimethy-Isilyl)hdroxylamine, 1-{trimethylsilyl)imidazole, trimethylsilylisocyanate, (trimethylsilyl)methyl acetate, trimethylsilyl methacrylate, (trimethylsilyl)methylamine, N-(trimethylsilylmethyl)urea, 4-(trimethylsilyl)morpholine, 4-(triethoxysilyl)butyronitrile, 1-(trimethylsilyl)pryrrolide, 1-trimethylsilyl-1,2,4-triazole, triphenyisilane, 5 triphenylsilandiol, triphenylsilylamine, tricyclohexylsilylamine, phenyl-dimethoxysilylamine, methylphenyldimethoxysilane, phenyldiethoxysifylamine, cyclohexyldimethoxysilylamine, cyclohexyldiethoxysilyiamine, dipheny-Imethoxysilylamine, diphenylethoxysilylamine, dicyclohexylmethoxysilylamine, dicyclohexylethoxysilylamine, cyclohexylsilyltriamine, cyclohexyl(ethyl)silyltri-1 o amine, cyclohexyl(methyl)silyltriamine, benzylsilyltriamine, benzyl(methyl)silyltriamine, diphenytsilyldiarnine, phenylethoxysilyldiamine, cyclohexylethoxysilyldiamine, cyclohexyldiethoxysilylamine, cyclohexylmethoxysilyldiamine, cyclohexyl(ethyl)ethoxysilyldiamine, cyclohexyl(methyl)ethoxysilyldiamine, benzylmethoxysilyldiamine, benzyl-15 dimethoxysilylamine, tris{trimethylsilyl)amine, tris(trimethoxylsilyl)amine, tris(triethoxylsilyl}amine, tris(trimethylsilyl)borate, tris{trimethylsilyl)methane, tris(trimethylsilyl}ethane, tris(trimethylsilyl)phosphate, tris(trimethylsilyl)phosphine, tris(trimethylsilyl)silane, vinyltriethoxysilane, vinyltrichlorosilane, vinyl-triisopropylsilane, vinyltrimethylsilane, vinyltri-2 0 phenylsilane, vintris(2-buytlidenaminooxy)silane, vinyltris(2-methoxyethoxy~
silane), vinyltris(trimethylsiloxy)silane, allyldimethylsilane, allyldiethylsilane, diallyldimethylsilane, diallyldiethylsilane, allyoxytrimethylsilane, allyoxytriethylsilane, allylphenylsilicon, tripropylsilane, tris(trimethylsilyl)silane, pentamethylcyclopentasiloxane, 2,4,6,8,10-2 5 pentamethylcyclopentasiloxane, pentamethyldisiloxane, amyltriethoxysilane, vinyltricholorsilane, vinyltriethylsilane, vinyltrimethylsilane, vinyltriphenylsilane, vinyltriethoxysilane, vinyltripropyoxysilane, vinyltrisopropyoxysilane, vinyitri-methoxylsilane, vinyltriphenoxysilane, vinyltributoxysilane, vinyltriisobutoxysilane, vinyltrisecbutoxysilane, vinyltri-tert-butoxysilane, 3 o vinyltris(2-butylidenaminooxy)silane, vinyltris(2-methoxyethoxy)silane, vinyltris(trimethoxysiloxy)silane, N,N-dimethyitrimethylsilyamine, N,N-diethyltrimethylsilyamine, 3,3-dimethyl-1-trimethylsily-1-butyne, 3,3-diethyl-trimethylsily-1-butyne, dimethyltrimethylsifylmethylphosphonate, dimethyltri-methylsilylphosphite, dimethyltritylbromosilane, dimethyl-vinyl-ethoxysilane, 35 dimethylvinylchlorosilane, diphenylmethylchlorosilane, diphenylethylchlorosilane, phenyldimethylchlorosilane, phenyldiethylchlorosilane, diphenyldi(M-tolyl)silane, 1,2-dimethylsilane, 1,2-diethylsilane, 2,2,4,4,6,6-hexamethylcyclotrisilazane, N-WO 99!66009 PCT/US99l13751 benzyltrimethylsilylamine, chlorodimethyloctylsilane, trimethyloctylsilane, disiloxane, silicori nitride, disilane, dimethylsilanediol, trichlorocyclopentysilane, tris(isopropylthio)silane, chlorotrimethylsilane, chlorodimethylsilane, bis{chloromethyl)dimethylsilane, propyltrichlorosilane, trimethyl(pentafluorophenyl)silane, trichloro(1 H,1 H,-2H,2H-perfluorooctyl)silane, silicon tetraboride, silicon hexaboride, trimethyl-2-thienylsilane, (4-bromophenyl)trimethylsilane, 4-(trtmethylsilyl)phenol, 5-(trimethylsilyi}-1,3-cyclopentadiene, trimethylsilylmethylmagnesiumchloride, N,N-diisopropyltrimethylsilylamine, dicyclohexyl-methyl-silane, 1 o tetracyclohexysilane, 1,1,2,2,3,3,4,4,5,5-decaphenyl-6,6-dimethylcyclohexasilane, trimethylsilylpolyphosphate, trimethyl-silylpolyphosphite, including analogues, homologues, isomers and derivatives thereof.
Additional examples of acceptable silicon derivatives can be found in Silicon Compounds. Reaister and Review, Petrarch Systems, Inc. (1984), Frontiers of Organosilicon Chemistry, Bassindale, Gaspar, The Royal Society of Chemistry, (1991 ), incorporated herein by reference. Corresponding compounds of germanium, tin, titanium, zirconium, selenium, tellurium, are contemplated in the practice of this invention.
Non-limiting germanium derivative compounds include:
decamethylgermaniumocene {bis(pentamethylcyclopentadienyl)germanium), tertbutylgermanium, tetramethylgermanium, tetraethylgermanium, tetrapropylgermanium, tetraisopropylgermanium, tetrabutylgermanium, tetraisobutylgermanium, tetra-tert-butylgermanium, tetra-sec-butylgermanium, tetra-phenylgermanium, phenylgermanium, methylphenylgermanium, methylphenolgermanium, including analogues, homologues, isomers and derivatives thereof.
Non-limiting derivative tin compounds include: decamethylstannocene (bis(pentamethylcyclopentadienyl)tin), dibutyltin bis{2-ethylhexanoate), dibutyltin diacetate, dibutyloxotin (dibutyltin oxide), dimethyltin, diethyltin, dipropyltin, diisopropyltin, dibutyltin, diisobutyltin, di-tert-butyltin, di-sec-butyltin, di-phenyltin, tetramethyltin, tetraethyltin, tetrapropyltin, tetraisopropyltin, benzltriphenyltin, allyltributyltin, tetrabutyltin, tetraisobutyltin, tetra-tert-butyltin, tetra-sec-butyltin, 3 5 tetraphenyltin, tetramethoxytin, tetraethoxytin, tetrapropoxytin, tetraisopropoxytin, tetrabutoxytin, tetraisobutoxytin, tetra-tert-butoxytin, tetra-sec-butoxytin, tetraphenoxytin, trimethoxymethyltin, triethoxymethyltin, tripropoxymethyltin, triisopropoxymethyltin, tributoxymethyltin, triisobutoxymethyltin, tri-tent-butoxymethyltin, tri-sec-butoxymethyltin, triphenoxymethyltin, dibutyltin dichloride, dibutyltin dilaurate, dibutyltin dimethoxide, dibutyltin diethoxide, dibutyltin methoxide, dibutyltin ethoxide, tetrabutyltin, tetramethyltin, tetraethyltin, tetrapropyltin, tetra-tent-butyltin, allyldibutyltin, allyldiphenyltin, allyldiphenylstannane, dichlorodiphenyltin, diphenyltin acetate, tributyltineacetate, tributyltinechloride, tributyltincyanide, tributyltin ethoxide, tributyltin methoxide, tributyltinhydride, tributylvinyltin, triphenyltinchloride, triphenyltinhydroxide, triphenyltinhydride, tributyltin ethoxide, including analogue, homologue, isomer, and derivative thereof.
1o Non-limiting examples of phosphorus derivative compounds of this invention include: phosphoric acid esters, othrophosphoric acid esters, nuetral phosphate esters, tetrabutylphosphonium hydroxide, allyldiphenylphospine, diphenylphosphine, phenylphosphine, diphenyl phosphate, diphenylphosphine, diphenylphosphinic acid, diphenylethoxyphospine, diphenylmethoxyphospine, diphenylpropoxyphospine, diphenylisopropoxyphospine, diphenylbutoxyphospine, diphenyl-sec-butoxyphospine, diphenyl-tert-butoxyphospine, diphenyl-iso-butoxyphospine, dicyclohexylethoxyphospine, dicyclohexylmethoxyphospine, dicyclohexyipropoxyphospine, dicyclohexyfisopropoxyphospine, 2 o dicyclohexylbutoxyphospine, dicyclohexyl-sec-butoxyphospine, dicyclohexyl-tert-butoxyphospine, dicyclohexyl-iso-butoxyphospine, dicyclopentyiethoxyphospine, dicyclopentylmethoxyphospine, dicycfopentylpropoxyphospine, dicyclopentylisopropoxyphospine, dicyclopentylbutoxyphospine, dicyclopentyl-sec-butoxyphospine, 2 5 dicyclopentyl-tert-butoxyphospine, dicyclopentyl-iso-butoxyphospine, dicyclohexyl(ethyl)ethoxyphospine, dicyclohexyl(ethyl)methoxyphospine, dicyclohexyl(ethyl)propoxyphospine, dicyclohexyl(ethyl)isopropoxyphospine, dicyclohexyl(ethyl)butoxyphospine, dicyciohexyl(ethyl)-sec-butoxyphospine, dicyclohexyl(ethyl)-tert-butoxyphospine, dicyclohexyl(ethyl)-iso-~ o butoxyphospine, phenyldiethoxyphospine (diethylphenylphosphonite), phenyldimethoxyphospine, phenyldipropoxyphospine, phenyldiisopropoxyphospine, phenyldibutoxyphospine, phenyidi-sec-butoxyphospine, phenyldi-tert-butoxyphospine, phenyldiisobutoxyphospine, cyclohexyldiethoxyphospine, cyclohexyldimethoxyphospine, cyclohexyl-3 5 dipropoxyphospine, cyclohexyldiisopropoxyphospine, cyclohexyl-dibutoxyphospine, cyclohexyldi-sec-butoxyphospine, cyclohexyldi-tert-butoxyphospine, cyclohexyldi-iso-butoxyphospine, cyclopen-tyldiethoxyphospine, cyclopentyldimethoxyphospine, cyclopentyl-dipropoxyphospine, cyclopentyldiisopropoxyphospine, cyclopentyl-dibutoxyphospine, cyclopentyldi-sec-butoxyphospine, cyclopentyldi-tert-butoxyphospine, cyclopentyldiiso-butoxyphospine, cyclohexyl(ethyl)diethoxyphospine, cyclohexyl(ethyl}dimethoxyphospine, cyclohexyl(ethyl)dipropoxyphospine, cyclohexyl(ethyl)diisopropoxyphospine, cyclohexyl(ethyl)dibutoxyphospine, cyclohexyl(ethyl)di-sec-butoxyphospine, cyclohexyl(ethyl)ditert-butoxyphospine, cyclohexyl(ethyl)diiso-butoxyphos-pine, dimethyimethylphosphate, diethylmethylphosphate, diethylethyl-phosphate, dimethylethylphosphate, ethylenebis(diphenylphosphine), methyl-1 o dichlorophosphite, methyldichlorophosphate, methyldichlorophosphine, methyldiphenylphosphine, propylphosphonic anhydride, dimethylphosphine, diethylphosphine, dimethylphosphine, dipropylphosphine, diisopropyl-phosphine, dibutylphosphine, diisobutylphosphine, disecbutylphosphine, di-t-butylphosphine, diphenylphosphine, diphenylphosphate, diphenylphosphineoxide, diphenylphosphine oxide, diphenyl-phosphineselenide, dis(diethylamino)phosphine, dis(dimethylamino)phospine, dis(2-ethylhexyl)phosphate, dis(dimethylsilyl)phosphate, dis(dimethylsil-yl)phosphite, di(toly)phosphine, di(o-toly)phosphine, di(m-toly)phosphine, di(p-toly)phosphine, di(toly)phosphite, di(o-toly)phosphite, di(m-toly)phosphite, 2 o di(p-toly)phosphite, di(toly)phosphate, di(toly)hydrophosphate, di(toly)phosphonic acid [(CH3C6H4)2P(OH)], mono{toly)phosphonic acid [(CH3C6H4)P(OH)2], diethylphenylphosphine, diethylphenylphosphite, dipropylphosphite, diisopropylphosphite, dibutylphosophite, diisobutylphosophite, di-sec-butylphosophite, di-tert-butylphosophite, 2 5 diphenylphosphite, allydiphenylphosphonium, allydiphenyfphosphonium hydride, allydiphenylphosphonium hydroxide, allydiphenylphosphonium chloride, dimethylphosphoramidous dichloride, hexamethylphosphoramide, hexamethylphosphorus diamide, hexamethylphosphorus triamide, 3o hexamethylphospophorimidic triamide, trimethylphosphine, trimethylphospate, trimethylphosphite, triethylylphosphite, tripropylphosphite, triisopropylphosphite, tri-butyl-phosphite, tri-iso-butylphosphite, tri-sec-butylphosphite, tri-tert-butylphosphite, triphenylphosphite, dimethylphosphite, diethylphosphite, dipropylphosphite, diisopropylphosphite, dibutylphosphite, 35 diisobutylphosphite, di-sec-butylphosphite, di-tert-butylphosphite, diphenyl-phosphite, dimethyiethylphosphine, dimethylethylphosphate, dimethylethylphosphite, diethylmethylphosphite, dipropylmethylphosphite, diisopropylmethylphosphite, di-butyl-methylphosphite, di-iso-butylmethylphosphite, di-sec-butylmethylphosphite, di-tert-butylmethylphosphite, diphenylmethyl phosphate, dimethylphosphonate, diethylphosphonate, dipropylphosphonate, diisopropylphosphonate, di-butyl-phosphonate, di-iso-butylphosphonate, di-sec-butylphosphonate, di-tert-butylphosphonate, diphenylphosphonate, dimethylmethylphosphonate, dimethylethylphosphonate, diethylmethylphosphonate, dipropylmethylphosphonate, diisopropylmethylphosphonate, di-butyl-methylphosphonate, di-iso-butylmethylphosphonate, di-sec-butylmethylphosphonate, di-tert-butyfmethylphosphonate, diphenylmethyl 1 o phosphonate, diethylethylphosphonate, dipropylethylphosphonate, diisopropylethylphosphonate, di-butyl-ethylphosphonate, di-iso-butylethylphosphonate, di-sec-butylethylphosphonate, di-tert-butylethylphosphonate, diphenylethyl phosphonate, dimethylcarbophosphonate, diethylcarbophosphonate, dipropyl-carbophosphonate, diisopropylcarbophosphonate, di-butyl-phosphonate, di-iso-butylcarbophosphonate, di-sec-butylcarbophosphonate, di-tert-butylcarbophosphonate, diphenylcarbophosphonate, dimethyl-methylcarbophosphonate, dimethylethylcarbophosphonate, diethyl-methylcarbophosphonate, dipropylmethylcarbophosphonate, diisopro-2 o pyimethylcarbophosphonate, di-butyl-methylcarbophosphonate, di-iso-butylmethylcarbophosphonate, di-sec-butylmethylcarbophosphonate, di-tert-butylmethylcarbophosphonate, diphenyimethyl phosphonate, diethylethylcarbophosphonate, dipropylethylcarbophosphonate, diisopropylethylcarbophosphonate, di-butyl-ethytcarbophosphonate, di-iso-2 5 butylethylcarbophosphonate, di-sec-butylethylcarbophosphonate, di-tert-butylethylcarbophosphonate, diphenylethyl phosphonate, dimethylphospite, dimethylphosphite, trimethyl phosphonoacetate, trimethyl 2-phosphonoacrylate, trimethyf phosphonoformate, trioctylphosphine oxide, triphenyl phospate, 3 o triphenylphosphine, triphenylphosphine oxide, triphenylphosphine-copper hydride, triphenylphosphine hydrobromide, triphenylphosphine dibromide, triphenylphosphine oxide, triphenylphosphine selenide, triphenylphosphine sulfide, tripiperidinophosphine oxide, tris(2-ethyihexyl)phosphate, 35 tris(dimethylamino)phosphine, tris(hydroxymethyl)aminomethane phosphate, tris(trimethylsilyl)phosphate, tris(trimethylsilyl)phosphite, tri(toly)phosphines (e.g. tri(o toly)phosphine, trim-toly)phosphine, trip-toly)phosphine), tri{toly)phosphite (e.g. tri(o-toly)phosphite, tri{m-toly)phosphite, trip-to-ly)phosphite), tri(toly)phosphate, tri(toly)hydrophosphate, tri(toly)phosphonic acid [(CH3C6H4)3P(OH)2], bis(2-ethylhexel) phosphate, diallyphenyl-phosphine, dibenzylphosphite, dibenzylphosphate, dibutyl phosphate, dimethyl methylphosphonate, dimethyl methylphosphine, dimethyl methylphosphonite, dimethylphenylphosphine, dimethylphenylphosphonite, dimethylphenyl-phosphite, dimethylphosphinic acid, dimethyl(trimethylsilyl-methyl)phosphonate, dimethyl trimethylsilyl phosphate, dimethyl trimethylsilyl phosphonate, ethyldiphenylphosphonite, diphenyl(2-methoxyphenyl)phosphine, to manganese (II) hydrogen phosphate, disodium fluorophosphate, disodium fluorophosphite, disodiumhydrogenphosphite, trisodium phosphate, trisodium phosphate, dipotassiium fluorophosphate, dipotassium fluorophosphite, tripotassium phosphate, tripotassium phosphate, ethyldiphenylphosphine, ethyldiphenylphosphinite, ethyldiphenylphosphonate, methyldiphenylphosphine, methyldiphenylphosphinite, methyldiphenylphosphonate, phenylphosphine, phenylphosphonic acid, phenylphospate phosphorus acid, phosphoric acid, phosphorus trichloride, phosurea, phosphorus trisulfide, tributyl phosphate, tributylphosphine, tri-tert-butylphosphine, tributylphosphine oxide, tributylphosphite, tris(2,4-di-tert-2 o butylphenyl)phosphite, tris(nonlphenyl)phosphite, phosphorous acid triphenylester with propane 1,3-diol, tris(2,2,2-trifluoroethyl)phosphite, tris(2-chloroethyl)phosphite, tris(1-chloroethyl)phosphite, trichlorophosphite, tris(tridecyl)phosphite, isooctyldiphenylphosphite, diisodecylphenylphosphite, triethyl 4-phosphonocrotonate, trimethyl 4-phosphonocrotonate, triethyl-2 5 phosphonoacetate, trimethylphosphonoacetate, trimethyl 2-phosphono-butyrate, triethyl 2-phosphonobutyrate, trimethylphosphonoformate, triethylphosphonoformate, trimethylphosponopropionate, trimethyl-phosponopropionate, tricyclohexylphosphite, tricyclohexylphophine, triethylphosphine, triethylphosphite, trimethylphosphine, triethylphosphate, tri-3 o methylphosphate, tripropylphosphate, triisopropylphosphate, tributyl-phosphate, triisobutylphosphate, tri-sec-butylphosphate, tri-tert-butylphosphate, triphenylphosphate, dimethyfphosphate, diethylphosphate, dipropylphosphate, diisopropylphosphate, dibutylphosphate, diisobutylphosphate, di-sec-butylphosphate, di-tert-butylphosphate, 35 diphenyimethylphosphate, diphenylethylphosphate, diphenylpropylphosphate, diphenylisopropylphosphate, dimethylethylphosphate, diethylmethyfphosphate, dipropyimethylphosphate, diisopropylmethylphosphate, di-butyl-methylphosphate, di-iso-butylmethyiphosphate, di-sec-butylmethylphosphate, di-tert-butylmethylphosphate, diphenylmethyl phosphate, triethylphosphoramide, trimethylphosphoramide, tripropylphosphoramide, triisopropylphosphoramide, tributylphosphoramide, triisobutylphosphoramide, tri-sec-butylphosphoramide, tri-tert-butylphosphoramide, triphenylphosphoramide, dimethoxyphosphorus-amide (CH30)2PNH2), diethoxyphosphorusamide, dipropoxyphosphorus-amide, diisopropoxyphosphorusamide, dibutoxyphosphorusamide, di-isobutoxyphosphorusamide, di-sec-butoxyphosphorusamide, di-tert-butoxyphosphorusamide, diphenoxyphosphorusamide, dimethylphosphor-lo amide (CH30)2PONH2), diethylphosphoramide, dipropylphosphoramide, diisopropylphosphoramide, dibutylphosphoramide, diisobutylphosphoramide, di-sec-butylphosphoramide, di-tert-butylphosphoramide, diphenylphosphoramide, dimethylethylphosphoramide, diethylmethyl-phosphoramide, dipropylmethylphosphoramide, diisopropylmethyl-phosphoramide, di-butyl-methylphosphoramide, di-iso-butylmethyl-phosphoramide, di-sec-butylmethylphosphoramide, di-tert-butyl-methylphosphoramide, diphenylmethyl phosphoramide, triethylcar-bophosphate, trimethylcarbophosphate, tripropylcarbophosphate, triisopropylcarbophosphate, tri-butyl-phosphate, tri-iso-butylcarbophosphate, 2 o tri-sec-butylcarbophosphate, tri-tart-butylcarbophosphate, triphenylcar-bophosphate, dimethylcarbophosphate, diethylcarbophosphate, dipropylcarbophosphate, diisopropylcarbophosphate, dibutylcarbophosphate;
diisobutylcarbophosphate, di-sec-butylcarbophosphate, di-tert-butylcarbophosphate, diphenylcarbophosphate, dimethylethylcarbophosphate, diethylmethylcarbophosphate, dipropyl-methylcarbophosphate, diisopropylmethyicarbophosphate, di-butyl-methylcarbophosphate, di-iso-butyimethylcarbophosphate, di-sec-butylmethylcarbophosphate, di-tart-butylmethylcarbophosphate, diphenylmethyl phosphate, dimethylvinylphosphate, diethylvinylphosphate, 3o dipropylvinylphosphate, diisopropylvinylphosphate, dibutyivinyiphosphate, diisobutylvinylphosphate, di-sec-butylvinylphosphate, di-tert-butyfvinyiphosphate, diphenylvinylphosphate, triisobutylphosphine, triisodecylphosphite, triisopropylphosphite, dibenzyldiethylphosphoramidite, dibenzyldiisopropylphosphoramidite, dibenzylphosphite, dibenzylphosphate, tris(tridecyl)phosphite, tritolylphosphate, tritolyphophine, tritolyphosphite, tricyclohexylphosphine, aliminum phosphate, 1,2-bis(diphenylphos phino)propane, trioctylphosphine oxide, trioctylphosphine, dichloromethylphosphine, dichlorophosphineoxide (C12P0), ethyidichlorophosphite, tetraethylpyrophosphite, benzyldiethylphosphite, benzyldiethoxyphosphorus, cyclohexyldiethoxyphosphorus, dibenzyldiisopropylphosphoramite (dissopropyl-phosphoraramidous acid dibenyl ester), di-tert-butyl diisopropylphosphoramidite, tert-butyl tetraisopropylphosphorodiamidite, (+I-)-1-amino-cis-3-phosphonocyciopentanecarboxlic acid, diallyl diisopropylphosphoramide, tert-butyl tetraisopropylphosphorodiamite, (1-amino-butyl)-phosponic acid, 6-amino-1-hexyl phosphate, 1-aminoethylphosponic acid, 2-aminoethyl dihydrogenphosphate, 2-aminoethylphosponic acid, methyl N,N,N'-to tetraisopropylphosphordiamidite, hexamethylphosphoramide [(CH3)2N]3P0, hexamethylphosphortriamidite [(CH3)2N]3P, diethyl 4-aminobenzylphosphonate, diethyl 4-aminobenzylphosphite, diethyibenzylphosphonate, diethylbenzylphosphite, tetraethylbenzylphosphonate, diethyl (pyrrolidinomethyl)phosphonate, diethyloxyphosphinyl isocyanate, 6-amino-1-hexylphosphate, diethyloxyphinyl isocyanate, diethylcyanomethylphosphonate, diethyfveinylphosphonate, dioctylphenylphosphonate, ethylphenylphosphinate, ethylphenylphosphonic acid, methylphosphonic acid, ethylphosphonic acid, propylphosphonic acid, isopropylphosphonic acid, butylphosphonic acid, sec-butylphosphonic acid, 2 o tert-butylphosphonic acid, isobutylphosphonic acid, phenylphosphonic acid, phenylphosphoric acid, phenylphosphinic acid, methylphenylphosphinate, methylphenylphosphine, aminomethylphosphonic acid, vinylphosphonic acid, hypophosphorus acid, sodium hypophosphate, sodium dihydrogenphosphate, fluorophosphoric acid, ammonium hydrogenphosphate, ammonium hydrogenphosphite, ammonium hydrogen-phosphine, lithiumdihydrogenphosphate, triphenylphosphineselenide, phosphoric acid, phosphorus oxychloride, phosphorus pentasuifide, metaphosphoric acid, phenylphosphate disodium salt, nitrilotris(methylene)triphosphonic acid, ethylenephosphite, 3o ammonium salt benzylphosphite, potassiumhexafluorophosphate, diethyltrimethylsilylphosphite, diethyl(trichloroethyl)phosponate, dimethyl(trimethylsilyl)phosphite, tris(trimethylsilyl)phosponate, 2-chloro-1,3,2-dioxaphospoJane, 2-chloro-1,3,2-dioxaphosphoiane-2-oxide, dimethylmethylphosphonate, diethylmethylphosphonate, 3 5 dimethylethylphosphonate, diethylethylphosphonate, ethylmethyl-phosphonate, 2-carboxyehtylphosphonic acid, 2,2,2-trichloro-1,1-dimethylethyldichlorophosphite, bis(2-chloroethyt)phosphoramidic dichloride, butyldichlorophosphite, butylphosphonic dichloride, tert-butylphosphonic ZOJ
dichloride, tent-butyldichlorophosphine, trimethylphosphonoformate, trimethylprapionamtde, trimethylpropionanilide, diethylchlorophosphate, diethytchtorophosphite, chlorodiethylphosphine, diethylphosphoramidous dichloride, diethylthiophosphate, sodium salt diethylthiophosphate, diethyl-phosphoramidate, dimethylphosphoramidate, tetramethylphosophorodiamidic chloride, tetramethylphosphonium chloride, diethylcyanophosphate, diethylcyanophosphonate, diethylcyanomethylphosphonate, diethoxyphosphinyl isocyanate, O,O'-diethytmethylphosphonothioate, diethytmethylphosphonate, diethyl(hydroxymethyl)phosphonate, to dimethyltrimethylsilylphosphite, 1-ethyl-3-methyl-1H-imidzolium hexaflurophosphite, diethylcyanmethylphosphonate, phosphorus napthenate, methylphenylphospholene, methylphenylphosolenedichloride, (aminobe-nzyl)phosphonic acid (e.g. (4-aminobenzyl)phosphonic acid), cyclophosphamide, pinacolytmethylphosphonate, diethyl(ethylthio-methyl)phosphonate, 2-furyl tetramethylphosphorodiamidite, diisopropylcyanomethylphosphate, 1,3,5-tris(2-hydroxyethyl}cyanuric acid, tris(2,4,-di-tert-butylphenyl)phosphite, tris(tridecyl)phosphite, tris(nonylphenyl)phosphite, phosphorus anyhydride, phospham, phosphonium chloride, phosphoniumsulfide, phosphoniumsulfate, phosphoramide, phor-2o phoramidite, metaphosphoramide, phosphorus chloride(di)nitride, phosphorus cyanide, phosphorus trifluoride, phosphorus pentafluoride, phosphorus oxybromide, phosphorus pentaselenide, phosphorus trioxide, phosphorus sesquioxide, phosphorus tri(tetra-)selenide, phosphorus thiochloride, phosphorus thiocyanate, hypophosphorus acid, metaphosphorus acid, 2 5 orthophosphorus acid, pyrophosphorus acid, phosphine, phosphorus nitride, phosphorus sesquisulfide, including analogues, homologues, isomers and derivatives thereof. The corresponding compounds of arsenic, antimony and bismuth are contemplated.
Non-limiting antimony derivative compounds include:
3 o alkyl antimony compounds, trialkyl compounds, cyclomaticlring system compounds, including, trimethylantimony, triethylantimony, tripropylantimony, triisopropylantimony, tributylantimony, triisobutylantimony, tri-tert-butylantimony, tri-sec-butylantimony, tri-phenylantimony, phenylantimony, tri(methylphenyl)antimony, triphenylantimony oxide, 35 tri(methylphenot)antimony, antimony ethoxide, pentamethytantimony, phenyldimethylantimony, phenylstibinic acid, tetramethyldistibyl, tributylstibene, triethylantimony, triethylantimony chloride, trimethylantimony, triphenylantimony, triphenylantimony dichloride, triphenylantimony sulfide, including analogue, homologue, isomers and derivative thereof.
Non-limiting arsenic derivative compounds include:
alkyl arsenic compounds. dialkyl compounds, cyciomaticlring system compounds including, diethylarsine, dimethylarsine, diphenylarsine, ethylarsine, methyiarsine. oxophenylarsine, triethylarsine, triethylarsine, tripropylarsine, triisopropylarsine, tributylarsine, triisobutylarsine, tri-tert-butylarsine, tri-sec-butylarsine, tri-phenylarsine, phenylarsine, tri(methyl-phenyl)arsine, triphenylarsine oxide, tri(methylphenol)arsine, phenylarsenic acid, phenylcyclotetramethylenearsine, arsenobenzene, cacodylic acid, 1 o cacodyl oxide, cacodyl amide, carbasone, arsanilic acid, ethanearsonic acid, methanearsonic acid, nitarsone, benzenearsonic acid, propyl arsonic acid, dimethylchlor-arsine, dimethylcyanoarsine, diphenylarsinic acid, diphenylchloro-arsine, ethylarsonic acid, methylarsine, methyldichloroarsine, phenylarsine, phenyldimethylarsine, tetraethyldiarsine, tetramethylbiarsine, tribenzylarsine, trimethylarsine, triethylarsine, tributyl arsine, tri-isobutyl arsine, triphenyl arsine, including analogue, homologue, isomers and derivative thereof. See Orpano Arsenial Compounds, Raiziss, Gavron, American Chemical Society (1923) and relatedlsubsequent editions, volumes or supplements, incorporated by reference. Corresponding compounds of 2o phosporus, antimony, bismuth are also contemplated herein and incorporated by reference.
Non-limiting bismuth derivative compounds include: alkyl bismuth compounds, dialkyl compounds, cyclomaticlring system compounds including, triphenylbismuth, triphenylbismuth carbonate, diphenylbismuthine, 2 5 methylbismuthine, triethyibismthine, trimethylbismthine, triphenylbismuthine, tri-n-propyibismuth, including analogue, homologue, isomers and derivative thereof.
Non-limiting potassium derivative compounds of this invention include:
potassium bis(dimethylsilyl)amide, potassium acetamide, potassium 3o bis(trimethylsilyl)amide, oxamic acid, P-aminosalicylic acid potassium salt, potassium salt 5-nitroorotic acid, potassium D-gluconate, potassium hexacyanoferrate(III) (K3Fe(CN)6), potassium diphenylphosphide, potassiumetherate, potassium acetate, potassium acetate acid, potassium salt acetic acid, potassiumbenzamide, potassium azide, potassium 35 antimonide, potassium orthoarsenate, potassium orthoarsenite, potassium meta-arsenite, potassium diborane, potassium pentaborate, potassium dihydroxy diborane, potassium borohydride, potassium anilide, potassium radium iodide, potassium chloride, potassium calcium chloride, potassium carbide, potassium carbonate, potassium hydrogen carbonate, potassium carbonate, potassium alkyl carbonates (alkyl potassium carbonates), potassium methyl carbonate, potassium ethyl carbonate, potassium propyl carbonate, potassium isopropyl carbonate, potassium carbonyl, potassium s cobalt (II) cyanide, potassium cobalt (III) cyanide, potassium cobaltinitrite, potassium cynomanganate (ll), potassium cynomanganate (III), potassium citrate, potassium ferricyanide, potassium ferrocyanide, potassium hydride, potassium hydroxide, potassium manganate, potassium permanganate, potassium methionate, potassium napthenate, potassium nitride, potassium 1 o nitrate, potassium nitrite, potassium nitrophenoxide, potassium nitrobenzene (e.g. potassium-p-nitrobenzene)potassium oleate, potassium oxalate, potassium oxalatofen-ate (II), potassium oxalatoferrate {III), potassium monoxide, potassium oxide, potassium peroxide, potassium mono-orthophosphate, potassium hypophosphite, potassium orthophosphate, i5 potassium hydroxoplumbate, potassium rhodium cyanide; potassium selenide, potassium selenite, potassium selenocynate, potassium selenocyanoplatinate, potassium disilicate, potassium metasilicate, potassium sodium carbonate, potassium sodium ferricyanide, potassium hydroxostannate, potassium disufide, potassium hydrosulfide, potassium 2 o pentasulfide, potassium tetrasulfide, potassium trisulfide, potassium telluride, potassium thioarsenate, potassium thioarsenite, potassium trithiocarbonate, potassium thiocyanate, potassium amide, potassium salt (E,E)-2,4-hexadienoic acid, dipotassium fluorophosphate, dipotassium fluorophosphite, tripotassium phosphate, tripotassium phosphate, potassium perchlorate, 2 5 propanoic acid potassium salt, potassium formate, potassium cyanate, potassium hexacyanocobaltate (III), potassium hypophosphite, potassium hexaflurorsilicate, potassium nitroprusside, potassium phenoxide, Shell Chemical's "SparkAid or SparkAde," potassium phosphate (dibasic, monobasic, tribasic), potassium salicylate, potassium selenide, potassium 3o tetracyanonickelate (II), potassium tetrafluoroborate, potassium xanthogenate, potassium -p-aminobenzoate, potassium copper ferrocynanide, potassium cupric ferrocyanide, potassium hexafluorophosphate, potassium hexanitricobaltate lli, potassium naphthenate, potassium-B-naphthoxide,potassium polysulfide, potassium 35 sodium phosphate, potassium stearate, potassium sulfide, potassium sulfite, potassium sulfate, potassium thiocyanate, potassium xanthate, potassium fluorosilicate, N-potassiumethylenediamine, oxalic acid dipotassium salt, potassium beta-hydropyruvic acid, potassium 1,1-dimethylurea, potassium 1,1-diethylurea, potassium 1,1-diepropylurea, potassium xanthate; potassium ethylxanthate, potassium methyfxanthate, potassium salt thiophenol, potas-siumaluminum-tri-tert-butoxide, potassium ferrosilicon, tri-phenyimethylpotassium, methylpotassium, ethylpotassium, potas-siumethynyl(acetylide), propylpotassium, isopropylpotassium, butylpotassium, isobutylpotassium, secbutylpotassium, tertbutylpotassium, pentapotassium, hexylpotassium, heptapotassium, amylpotassium, isoamylpotassium, benzylpotassium, dimethylbenzylpotassium, tolylpotassium, dodecylpotassium, cyclopentadienylpotassium, 1 o methylcyclopentadienylpotassium, cyclohexylpotassium, potassiumheptyl, potassiumdodecyl, potassium tetradecyl, potassium hexadecyl, potassium octadecyl, phenylpotassium, potassium o-tolyl, potassium m-tolyl, potassium p-tolyl, potassium-p-chlorophenyl, potassium p-bromophenyl, potassium potassium o- anisyl, potassium m-anisyl, potassium p-anisyl, potassium diethoxyphenyl, potassium dimethoxyphenol, potassium m-cumyl, potassium p-ethoxyphenyl, potassium m-dimethyfaminophenyl, potassium 9-flourene, potassium a-napthyl, potassium b-napthyl, potassium p-phenylphenyl, potassium 9-phenylanthryl, potassium 9-anthryl, potassium 9-methylphen-anthryl, potassium pyridyl, potassium 2-pyridyl, potassium 3-pyridyl, 2 o potassium 6-bromo-2-pyridyl, potassium 5-bromo-2-pyridyl, potassium diben-zofuryl, potassium 3-quinoyl, potassium 2-lepidyl, potassium triphenylmethyl, potassium 2,4,6-trimethylphenyl, potassium 2,4,6-triisopropylphenyl, potassium 2,3,5,6-tetraisopropylphenyi, potassium tetrabutylphenyl, thiophenedipotassium, toluenedipotassium, diphenylethyienedipotassium, 2 5 potassiumamylethynyl, potassiumphenylethynyl, potassiummethoxybromophenyl, potassium phenylisopropyl, potassium tetraphenylboron, potassium tetramethylboron, potassium a-thienyl, potassium m-trifluoromethylphenyl, phenylethynylpotassium, 3-furylpotassium, phenylisopropylpotassium, dibenzofuranylpotassium, 3 o potassium dimethylbenzyl, potassium selenocyanate, potassium trimethylsilanolate, diphenylphosphide, potassium benzoate, potassium tert-butyl carbonate, potassium azide, di-potassiumcyanamide, potassium cyanide, potassium dicyanamide, cyclohexanebutyric acid potassium salt, cyclohexane acid potassium salt, cyclopentadientylpotassium, potassium tri-35 tert-butoxyaiuminum hydride, potassium triethylborohydride, potassium trirnethylborohydride, potassium tripropylborohydride, potassium triisopropylborohydride, potassium tributylborohydride, potassium triisobutylborohydride, potassium tri-sec-butylborohydride, potassium tri-tert-butylborohydride, potassium trisiamylborohydride, potassium chlorate, potassium tert-butoxide, potassium sec-butoxide, iso-butoxide, potassium antimonate, potassium diphenylphosphide, potassium bis(trismethylsilyl) amide, tripotassium phosphite, potassium selenocyanate, potassium tri-sec-butylborohydride, potassium triethylsilanolate, potassium thiocyanate, potassium acetylide, potassium chlorate, potassium salicylate, potassium di-potassium tetracarbonylferrate, potassium tetraphenylborate, potassium triethylborohydride, potassium triacetoxyborohydride, potassium triphenylborane, potassium hydroxide, potassium diphenylphosphide, to potassium methoxide, potassium ethoxide, potassium tri-sec-butylborohydride, tri-tert-butylborohydride, potassium triethylborohydride, potassium triphenylborohydride, potassium trisiamylborohydride, potassium metavanadate, potassium cyclohexanebutyrate, potassium hexachloro-platinate, potassium thiocyanate, potassium selenocyanate, potassium cyanate, potassium floride, potassium hexafluoroantimonate, potassium hexafluoroaluminate, potassium hexafluoroarsenate, potassium hexafluorosilicate, potassium hexacyanocobalt(II)ferrate(II), dipotassiumhexacyanocobalt(II)ferrate(II), potassium hexafluorotitanate, potassium hexafluorozirconate, potassium hexahydroxyantimonate, 2 o potassium hexachlororuthenate, potassium hexachloropalladate, potassium formate, potassium tetracyanonickelate, potassium tetrafluoroaluminate, potassium tetrafluoroborate, potassium thioacetate, L-glutamic acid mono-potassium salt, fumaric acid potassium salt, oxamic acid potassium salt, potassium salt Biphenyl-phospane, P-aminobenzoic potassium salt, aminobenzole acid potassium salt, alpha-napthaleneacetic acid potassium salt, dipotassium salt 2,6-naphthalenedicarboxlic acid, potassium cyclcohexanetherate, potassium phthalimide, P-aminosalicylic acid potassium salt, potassium salt 3,5-dimethylcyclohexyl sulfate, indolebutyric acid potassium salt,indole-3-butyric acid potassium salt, potassium 3o diphenylphosphide, potassium dimethylsilanolate, potassium triethylborohydride, potassium propoxide, potassium isopropoxide, potassium butoxide, potassium sec-butoxide, potassium pentoxide, potassium tert-pentoxide, potassium hydrogenphthalate, potassium oxalate, potassium hydrogensulfate, monopotassium acetylenedicarboxylic acid, potassium 3 5 pyrophosphate, potassium dihydrogenphosphate, potassium hexoate (potassium salt hexoic acid), potassium diphenylphosphide, potassium trimethylsifonalate, potassium phthalic acid, P-aminobenzoic acid potassium salt, monopotassium L-aspartic acid, tetraphenyldipotassium (C6H5)2CK2-10~
C(C6H5)2, potassiumethylphenyl (KCH2C6H5), potassium bromate, potassium chromate, potassium hydrogenphospate, monpotassium salt D-shaccharic acid, DI-asparatic potassium salt, (R)-alpha-hyroxymethylaspartic acid potassium salt, potassium fluoride, potassium iodate, potassium salt ethyl malonate, potassium thioacetate, potassium phenol, potassium salt aminobenzoic acid, potassium arninophenol salt, potassium cyclohexenol.
potassium methylcyciohexenol, potassium cyclopropanol, potassium methyl-cyclopropanol, potassium cyclobutanol, potassium methylcyclobutanol.
potassium methylcyclopentanol, potassium cyclopentanol, potassium 1 o cyclohexenol, potassium methylcyclohexenol, potassium dimethylcyclohexenols (e.g. potassium 3,5-dimethylcyclohexanol, potassium 2,3-dimethylcyclohexanol, potassium 2,6-dimethylcyclohexanol, potassium 2,5-dimethylcyclohexanol, 3,5-dimethylcyclohexanol), potassium o-ethylxanthic acid, monopotassium salt 2-ketoglutaric acid, dipotassium salt, ketomalonic acid, potassium salt lactic acid, dipotassium thiosulfate, potassium antimony tartrate, potassium dichloroacetate, potassium dimethyl-acetate, potassium diethylacetate, potassium dipropylacetate, potassium metaborate, potassium tetraborate, potassium tetrachlorocuprate, potassium acetoacetate, potassium diisopropylamide, potassium diethylamide, 2o potassium dimethylamide, potassium bis(dimethylsilyl)amide, dipotassium phthalocyanine, dipotassiumtetrabromocuprate, dipotassium tetrabromonickelate, dipotassiumtetrachloromanganate, dipotassiumbutadiyne, potassium cyclopentadienide, potassium dicyclohexylamide, potassium diethyiamide, potassium dimethylamide, potassium dipropylamide, potassium diisopropylamide, potassium thexylborohydride, potassium tri-tert-butoxyaluminohydride, potassium trimethylsilyl)acetyfide, potassium triethylsilyl)acetylide, potassium tris[(3-ethyl-3-pentyl)oxyJaluminohydride, (phenylethynyl)potassium, 2-thienylpotassium, potassium diethyldihydroaluminate, potassium 3o dimethyldihydroaluminate, potassium aluminum hydride, potassium bifluoride, potassium biphenyl, potassium biselenite, potassium bis(2-methoxyethoxy)-aluminum hydride, potassium bismuthate, potassium borate, potassium chlorite, potassium cobaltnitrite, potassium cyanoborohydride, potassium cyclopentadienide, potassium dicyanamide, potassium hexametaphosphate, potassium hexanitrocolbaltate, potassium hydrogenphosphite, potassium hydrogenselenite, potassium hydrogensulfite, potassium hydrosulfite, potassium hypochloride, potassium metaarsenite, potassium rnetabisuifide, potassium metaperiodate, potassium methacrylate, potassium nitroferricyanide, oxybate, potassium pentamethylcyclopentadienide, potassium phenolate, polyphosphate, potassium polyphosphite, potassium propionate, potassium pyrophosphate, potassium selenate, potassium selenite, potassium tetrachloroaluminate, potassium thiomethoxide, potassium thiosulfate, potassium thiosulfide, potassium thiosulfite, potassium triactoxyborohydride, potassium trimethylsilonate, potassium triethylsilonate, potassium tris(1-pyrazoly)borohydride, including analogues, homologues, isomers and derivatives thereof. Corresponding compounds of rubidium, caesium (cesium ), francium are contemplated in the practice of this invention.
to Non-limiting derivative magnesium compounds contemplated by this invention include: alkyl manganese compounds, dialkyl magnesium compounds, magnesium ethylate (ethoxide), magnesium methoxide, dimethylmagnesium, diethylmagnesium, dipropylmagnesium, diisopropylmagnesium, dibutylmagnesium, ditertbutyimagnesium, di-iso-butylmagnesium, di-sec-butylmagnesium, diphenylmagnesium, methylmagnesium chloride, methylmagnesium iodide, magnesium methylcarbonate, magnesium hydroxide, magnesium anthracene dianion, bromomagnesium isopropylcyclohexylamide, methylmagnesium bromide, methylmagnesium chloride, ethylmagnesium chloride, magnesium floride, 2 o magnesium chloride, butylmagnesium chloride, isopropylmagnesium chloride, cyclopentylmagnesiumhydride, cyclopentylmagnesiumhydroxide, cyclopentyl-magnesiumchloride, cyclopentylmagnesiummethyl, cyclopentylmag-nesiumethyl, cyclopentylmagnesiummethylol, cyclopentylmagnesiumethylol, cyclopentylmagnesiummethoxy, cyclopentylmag-nesiumethoxy,cyclohexylmagnesiumhydride, cyclohexylmagnesiumhydroxide, cyclohexylmagnesiumchloride, cyclohexylmagnesiummethyl, cyclohexylmag-nesiumethyl, cyclohexylmagnesiummethylol, cyclohexylmagnesiumethylol, cyclohexylmagnesiummethoxy, cyclohexylmagnesiumethoxy, tert-butyimagnesium chloride, isobutyl-magnesium chloride, allymagnesium 3o chloride, benzylmagnesium chloride, benzylmagnesium hydride, benzylmagnesium ethylate, benzylmagnesium methylate, benzylmagnesium ethoxy, benzyl-magnesium methoxy, magnesium acetate, magnesium alkyl carbonates, magnesium methyl carbonate, magnesium ethyl carbonate, magnesium isopropyl carbonate, trimethyisilylmethyl magnesium chloride, 3 5 magnesium acetate tetrahydrate, methylmagnesium isopropylcyclo-hexylamide, magnesium pyrophosphate, phenylethynylmagnesium bromide, methylphenylmagnesiumchloride, methylmagnesium, ethylmagnesium, propylmagnesium, isopropylmagnesium, butylmagnesium, isobutylmagnesium, tert-butylmagnesium, sec-butylmagnesium, phenylmagnesium, magnesium acetate, magnesium hydrogenphosphate, cyclopentylmagnesium, cyclopentylmagnesiumhydroxide, cyclopentylmethylmagnesium, methylcyclopentylmethylmagnesium, allylmagnesium, benzylmagnesium, pentylmagnesium, 1,1-dimethylpropylmagnesiumhydroxide, 1,1-dimethylpropylmethylmagnesium, phenylmagnesium, phenolmagnesium, magnesium hydroxide, magnesiumcarbonate, magnesiumsilicide, magnesium phosphate, magnesium phosphite, magnesium bisulfite, L-aspartic acid magnesium, DL-1 o aspartic acid magnesium, including analogue, homologue, isomer, and derivative thereof. Corresponding beryllium, calcium, strontium, barium, radium and zinc compounds are contemplated in the practice of this invention. See The Organic Compounds of Magnesium Beryllium Calcium Strontium. and Barium, loffe, Nesmeyanov, Amsterdam (1967), Orpanomagnesium Methods in Or~c~anic Synthesis, Wakefield, Academic Press, FL (1995), incorporated by reference. The mixture of dialkyl magnesium compounds with pyrophoric metallics is specifically contemplated.
Non-limiting selenium derivative compounds include: alkyl and dialkyl selenium compounds, dimethylselenium, dimethyl selenide, diethylselenium, 2 o dipropylselenium, diaisopropylselenium, diabutylselenium, diaisobutylselenium, dip-tert-butylselenium, dip-sec-butylselenium, di-phenylselenium, tetramethylselenium, tetraethylselenium, tetrapropylselenium, tetraisopropylselenium, tetrabutylselenium, tetraisobutyl-selenium, tetra-tert-butylselenium, tetra-sec-butylselenium, tetra-2 5 phenylselenium, phenylselenium, methylphenylselenium, methylphenylselenide, methylphenolselenium, zinc selenite, di-n-butylphosphane selenide, selenanthrene, selenourea, selenophene, allylphenylselenide, 1,3-dihydro-benzoimid-; 2,3-dihydro-3-methyl-, 1,1-dimethyl-2-selenourea, dipheny! diselenide, phenylselenyl chloride, 3 o benzeneseleninic acid, sodium selenite, benzeneseninic anhydride, potassium selenocyanate, selenourea, sodium hydrogenselenite, 4-chiorobenzeneseleninide, 4-(methylseleno)butyrate, benzyl selenide, alkyl selenium, including dimethylselenide, diethylselenide, dipropylseienide, etc., ally phenyl selenide, benzeneselenol, benzyl selenide, 35 (phenylselenomethyl)trimethylsilane, potassium selenate, potassium selenite, selenic acid, dibenzyl diselenide, p-tolyl selenide, triphenylphosphine selenium, seleno-DL-methionine, P-tolyl selenide, including analogue, homologue, isomer, and derivative thereof. See Organoselenium Chemistry, Liotta, John Wiiey & Sons, N.Y. (1987), incorporated herein by reference.
Non-limiting telluride derivative compounds include: di-n-butylphosphane selenide, selenanthrene, selenourea, selenophene, allylphenylselenide, dimethyltelluride, diethyltelluride, dipropyltelluride, diisopropyltelluride, dibutyltelluride, diaisobutyltelluride, dia-tent-butyltelluride, dia-sec-butyltelluride, di-phenyltelluride, tetramethyltelluride, tetraethyltel-luride, tetrapropyltelluride, tetraisopropyltelluride, tetrabutyltelluride, tetraisobutyltelluride, tetra-tart-butyltelluride, tetra-sec-butyltelluride, tetra-phenyltelluride, phenyltelluride, methylphenyltelluride, methylphenoltelluride, 1 o zinc selenite, di-n-butylphosphane telluride, diphenyl ditelluride, dimethyltel-luride, diethyltelluride, dipropylteliuride, diisopropyltelluride, dibutyltelluride, diisobutyltelluride, di-tart-butyltelluride, di-sec-butyltelluride, di-phenyltelluride, dimethylditelluride, diethylditelluride, dipropyiditelluride, diisopropylditelluride, dibutylditelluride, diisobutylditelluride, di-tart-butylditelluride, di-sec-butylditelluride, di-phenylditelluride, including analogue, homologue, isomer, and derivative thereof.
Non-limiting iron derivative compounds include: [cyclopentadienyl]
methylcyclopentadienyl iron, ferrocene, methylferrocene, and butadiene iron tricarbonyl, [butadiene iron tricarbonyl,] dicyclopentadienyl iron and 2 o dicyclopentadienyl iron compounds;ferrocene, rnethylferrocenes, decamethylferrocene (bis(pentamethyicyclopentadienyl)iron), 1,1'-diacetylferrocene, ferrocenecarboxylic acid, 1,1'-ferrocenecarboxylic acid, ferroceneacetic acid, ferroceneacetronitrile, 1,1'-ferrocene-bis(diphenylphosphine), ferrocenecarbonxaldehyde, ferrocenecarboxylic acid, 2 5 1,1'ferrocenedicarboxylic acid, 1,1'ferrocenedimethanol, ferrocenedimethanol, diiron nonacarbonyl, di-irondodecacarbonyl, di-ironnonacarbonyl, ironpentacarbonyl, triiron dodecacarbonyl, vinylferrocene, biscyclopentadienyl iron (ferrocene), cyclopentadienyl methylcyclopentadienyi iron, bis(methyl-cyclopentadienyl)iron, cyclopentadienyl ethylcyclopentadienyl iron, 3o bis(ethylcyclopentadienyl)iron, bis(dimethylcyclopentadienyl)iron,bis(trimethyl-cyclopentadienyl)iron, cyclopentadienyl tart-butylcyclopentadienyl iron, bis(pentamethylcyclopentadienyl)iron, methylcyclopentadienyl ethylcyclopentadienyl iron, bis(hexylcyclopentadienyl)iron, bisindenyl iron, butadiene iron tricarbonyl, dicyclopentadienyl iron, cyclopentadienyl iron (di 3s carbonyl) (iodide), cyciopentadienyl iron (carbonyl) (iodide) (methyltetra-hydrofuran), iron (III} ferrocyanide, ammonium hexacyanoferrate (II) hydrate, cyclopentadienyliron dicarbonyl dimer, cyclopentadienyliron dicarbonyl iodide, iron pentacarbonyl, diiron nonacarbonyl, ferroceneacetic acid, ferro-ceneacetonitrile, ferrocenemethanol, acetylferrocene, including analogue, homologue, isomer, and derivative thereof. Other examples are set forth U.S.
Patents 2,680,; 2,804,468; 3,341,311, The Organic Chemistry of Iran, Koemer, New York, Academic Press (1978), incorporated herein by reference.
Non-limiting nickel derivative compounds include:
alkyl, aryl, alkyloxy, alkylanol, aryloxy, diltriaikyl, diltriaryl, diltrialkyloxy, diltrialkylanol, diltriaryloxy, andlor cyclomatic complexes, including, bis-cyciopentadienyl nickel, cyclopentadienyl methylcyclopentadienyl nickel, 1o bis(methylcyclopentadienyl) nickel, bis(triphenylphosphine)dicarbonyi nickel, bis(isopropylcyclopentadienyl) nickel, bisindenyl nickel, cyclopentadienyl nickel nitrosyl, methyfcyclopentadienyl nickel nitrosyl, including analogue, homologue, isomer, and derivative thereof.
Non-limiting cobalt derivative compounds include: biscyclopentadienyl cobalt, bis(methylcyclopentadienyl) cobalt, bis(dimethylcyclopentadienyl) cobalt, cyclopentadienyl cobalt, dicarbonyl, cobalt(ous) hexamethylenetetramine, cobalt(ous) hydroxyquinone, cyclopentadienylcobalt dicarbonyf, including analogue, homologue, isomer, and derivative thereof.
Non-limiting zinc derivative compounds include: alkyl zinc, aryl zinc, 2 o alkyloxy zinc, aryloxy zinc, dialkyl zinc, diaryl zinc, dialkyloxy zinc, diaryloxy zinc, cyclomatic zinc complexes, including, dimethylzinc, diethylzinc, dipropylzinc, diisopropylzinc, dibutylzinc, diisobutylzinc, di-tert-butylzinc, di-sec-butylzinc, di-phenylzinc, zinc acetate, zinc ethoxide, zinc arsenide, zinc hydroxide, zinc selenide, zinc selenite, zinc flouride, zinc chloride, zinc 2 s cyanide, zinc floride, zinc chloride, zinc undecylenate, zinc nitrate, zinc acrylate, zinc methacrylate, methyl zinc chloride, isobutylzinc chloride, zinc stearate, zinc dimethyldiethiocarbamate, di-n-propylzinc, di-o-tolyzinc, isobutylzinc chloride, methylzinc chloride, zinc methacrlate, zinc acrylate, zinc hexaflourosilicate, zinc nitrate, zinc hydroxide, zinc undecylenate, zinc 3 o selenite, zinc cyanide, isobutylzinc chloride, methyl zinc chloride, L(+)lactic acid hemizinc, including analogues, homologues, isomers and derivatives thereof. Corresponding magnesium compounds are contemplated. See Zinc.
The Science and Technology of the Metal. Its Alloys & Compounds, Mattewson, N.Y., Reinhold (1959), incorporated by reference.
35 Non-limiting examples of transition metal derivative compounds, e.g.
metals of scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, and their respective chemical groups, include transition metal alkyl, aryl, alkyloxy, aryloxy, andlor ring system type compounds. Multiple alkyl, WO 99/66009 PCT/US99/13'151 alkyloxy radicals per metal are contemplate. Cyclomatic transition metal compounds are expressly contemplated. See Oraanometaliic Chemistry of Transition Metals, 2 Ed, Crabtree, John Wiley & Sons, N.Y. (1994), incorporated herein by reference.
Non-limiting examples of manganese compounds include benzyleyelopentadienyl manganese tricarbonyl; 1.2-dipropyl 3-cyclohexylcyclopentadienyl manganese tricarbonyl; 1.2-diphenyl-cyclopentadienyl manganese tricarbonyl; 3-propenylienyl manganese tricarbonyl; 2-tolyindenyl manganese tricarbonyl; fluorenyl manganese 1 o tricarbonyl; 2.3.4.7 - propyflourentyl manganese tricarbonyl; 3-naphthylfluorenyl manganese tricarbonyl; 4.5.6.7-tetrahydroindenyl manganese tricarbonyl; 3-3ethenyl-4, 7-dihydroindenyl manganese tricarbonyl; 2-ethyl 3 (a-phenylethenyl) 4,5,6;7 tetrahydroindenyl manganese tricarbonyl; 3 - (a-cyclohexylenthenyl) -4.7 - dihydroindenyl manganese tricarbonyl; 1,2,3,4,5,6,7,8 - octahydrofluorenyl manganese tricarbonyl and the like. A preferred cyclomatic manganese tricarbonyl is cyclopentadienyl manganese tricarbonyl. A more preferred cyclomatic manganese tricarbonyl is methyl cyclopentadienyl manganese (MMT).
Non-limiting examples of acceptable substitutes include the alkyl, aralkyl, 2 o aralkenyl, cycloalkyl, cycloalkenyl, aryl and alkenyl groups. The above compounds can be generally prepared by methods that are known in the art.
Corresponding compounds of technetium and rhenium (see Canadian Patent #1073207) are contemplated.
Non-limiting nitrogen derivative compounds include:
2-methoxybenzyfamine, 2-methoxybenzylarnine, 2-(4-methoxyben-zylamino)pyridine, nitroanline, 1-nitroanline, 2-nitroanline, 3-nitroanline, 4-nitroanline, nitroanisole, 1-nitroanisole, 2-nitroanisole, 3-nitroanisole, 4-nitroanisole, aniline, 2-anilinoethanol, anisamide, anisonitrile, acetonitrile, nitromethane, nitroethane, picoline, 1-picoline, 2-picofine, 3-picoline, 4-3o picoline, tetramethylammoniumhydroxide, dimethylolurea, 1,1-dibutylurea, tetraethylammoniumhydroxide, N,N,N',N'-tetramethylethylenediamine, toluic hydazide, toluidine, m-toluidine, o-toluidine, p-toluidine, tolunitrile, o-tolunitrile, p-tolunitrile, triazacyclononane, triazole, 1,2,4-triazole, triazine, 1,3,5-triazine, tributylamine, triethanofamine, trimethanolamine, tripropanolamine, trimethoxypyrimidine, 2,4,6-trimethoxypyrimidine, tetramethylammonium, trimethylpyrazine, urea, urazole, guanidine nitrate, guandine acetatic acid, thiophenol, sodium salt thiophenol, thiourea, cumidine, diphenylamine, m-xylidine, monmelthylanine, toluidine, amylaminobenzene, ethyiaminobenzene, aminophenyl, methyl-o-toluidine, n-butylaminobenzene, n-propyl-aminobenzene, monoethylaniline, mon-n-propylanifine, ethyldiphenylamine, mono-n-butylaniline, diethylamine, di-n-propylaniline, mono-isoamylaniline, diethyianiline, dimethylaniline, ethylamine, triethylamine, triphenylamine, s isopropylnitrite, ammonia, including analogues, homologues, isomers and derivatives thereof.
Non-limiting titanium derivative compounds include: titanium diisopropoxide bis(2,4-pentanedionate), titanium methoxide, titanium ethoxide, titanium (IV) 2-ethylexoxide, titanium isopropoxide, 1 o tetraethylorthotitanate, including analogues, homologues, isomers and derivatives thereof.
Non-limiting zirconium derivative compounds include: zirconium carbide, zirconium propoxide, zirconium ethoxide, decamethyfzirconocene, decamethylzirconocene dichloride, bis-cyclopentadienyl zirconium, including 15 analogues, homologues, isomers and derivatives thereof.
Non-limiting molybdenum derivative compounds include: molyb-denumcarbonyl, molybdenum hexacarbonyl, tripyridine tricarbonyl-molybdenum, molybdenumoxytetrachloride, cyclopentadienyl molybdenum carbonyls, including but not limited to benzenemolybdenumtricarbonyl, 2 o bicycloheptadienemolybdenum tetracarbonyl, cycloheptatrienmolybdenum tricarbonyl, bis-cyclopentadienylbimolybdenum pentacarbonyl, mesitylenemolybdenum tricarbonyl, tropeniummolybdenum tricarbonyl fluoroborate, cyclopentadienylmolybdenum tricarbonyl dimer, methylcyclopentadienylmolybdenum tricarbonyl dimer, anisoie molybdenum 2 s tricarbonyl, mesitylene molybdenum tricarbonyl, including analogue, homologue, isomers and derivative thereof. See U.S. Patents 3,272,606, and 3,718,444, incorporated by reference. Corresponding chromium and tungsten compounds are contemplated in the practice of this invention.
Non-limiting copper derivative compounds include: alkyl copper 3o compounds, bis(ethylenediamine)copper(II) hydroxide, copper carbonate, cyclopentadienyltriethylphosphine copper, diazoaminobenzene (ous), copper acetate, copper acetylacetonate, copper aminoacetate, copper ethylacetate, copper ferrocyanide, copper potassium ferrocyanide, copper nathenate, copper nitrate, copper phosphide, copper phthalate, including analogue, 3 5 homologue, isomers and derivative thereof. See Copper. The Science and Technology of the Metal. Its Alloys & Comaounds, Butts, N.Y., Reinhold (1954), incorporated by reference.

Other contemplated organometailic compounds are metallocenes, non-limiting example compounds include, ferrocene, cobaltocene, nickelocene, titanocene dichloride, zirconocene dichloride, uranocene, decamethyfferrocene, decamethylsificocene, decamethylgermaniumocene, decamethylstannocene, decamethylphosocene, decamethyiosmocene, decamethylruthenocene, decamethyizirconocene, including analogue, homologue, isomers and derivative thereof.
It is to be noted the above list is not exhaustive. The metals and their derivative compounds of this invention include every metal, metalloid, andlor 1 o non-metal (herein "metal" or "metallic") capable of acheiving vapor phase combustion, individually or incombination with Applicant's said ECS oxygen-ates.
Applicant's invention contemplates wide variation in metal substitution and mixing practice. Thus, it is expressly contemplated the non-lead organo-metallics, non-lead inorganic metallics, andlor their related high heat releasing compounds, including those set forth above may be mixed in varying proportions, andlor substituted andlor replaced by any non-lead metallic or non-metallic (organic or inorganic [atom, molecule or compound, including those containing nitrogen, sulfur, chlorine, fluorine, helium, neon, 2o argon, krpton, xenon, or radon atoms]) accomplishing the object of this invention.
Metal derivative compounds and combinations may be entirely or may contain in part or whole non-metal atoms, e.g. nitrogen, sulfur, chlorine, fluorine, helium, neon, argon, krpton, xenon, or radon, etc., so long as primary object of vapor phase combustion is accomplished. It is contemplated Applicant's metals are substitutents in the fuel, itself, which may also contain certain non-metals and their derivative compounds, including but not limited to nitrogen, sulfur, fluorine, chlorine, helium, neon, argon, krpton, xenon, or radon, in combination with dialkyl carbonates. These non-metals, and their 3 o derivative compound, may be employed with or without any other contemplated metals. It is further contemplated to substitute or mix these non-metallics with non-metallics, with metallics, or to mix metallics with metallics, etc., to achieve synergistic improvements in heat releases, burning velocity, thermal efficiency, emission reductions, power generation, and the like.
It is contemplated said non-metals will employed in varying proportions within the compound or combination compounds to achieve synergistic improvements in heat releases, burning velocity, thermal efficiency, emissions, power generation, and the like. For example, WO 99/6b009 PCT/US99/13751 hexamethylphosphoric triamide, N,N,N',N'-hexamethylsilanediamine, bis(diethylamono}-dimethylsilane may be added as a co-metallic or as a secondary co-combustion agent to the co-combustion agents set forth above.
Concentrations will be minor, but sufficient to further improve vapor phase combustion (e.g further enhancing fuel ecomony or power, etc.).
Ranges vary depending upon the specific metallic, fuels, fuel weight, regulations, advance applications, thermodynamics, and the extent combustion systems are modified to enhance the accelerated low temperature high energy nature of Applicant's invention. Thus, metallic 1o concentrations that maximize combustion velocity andlor the vapor phase combustion object of this invention are expressly contemplated.
However, it is contemplated that Applicant's fuel also be absent any metal or non-metal. That is, Applicant's invention, by accelerating burning velocity and/or increasing latent heat of vaporization, andlor reducing combustion temperatures by fuel substituent tailoring, chemical andlor mechanical means, as set forth herein or in the afforementioned PCT Applica-tions, said fuel can be employed absent either an ECS oxygenate or a metallic or non-metallic.
In accordance with this invention, Applicant's fuels will contain that 2 o amount of at least non-lead metallic, which constitutes a combustion improving amount consistent with the fuel composition, stoichiometry, combustion system, efficiencies, fuel economy and power desired, as well as legal and/or environmental considerations.
1t is expressly contemplated that Applicant's metallics be incorporated 2 5 into liquid fuel systems by means of mutual solvents, mutual dispersentslsolvents, colloidal media, suspension media, or other known means, or being separately injected. Metallic's, which are solid at ambiant temperatures may be introduced into the combustorlcombustion chamber by liquidification or gasification means.
3 o It is preferred the metailics of this invention be relatively inexpensive to manufacture on a mass production basis.
The metal and concentration amounts are to be optimized, such that vapor phase combustion results. Thus, the metal and its optimum concentration amount, is an amount that results in vapor phase combustion, 35 which is evidenced by improved fuel economy, emissions, power, etc. In the practice of this invention, the ratio of oxygenated ECS compound by weight to elemental metal by weight in the composition is equal to or less than 10,000:1 (parts) to equal or greater than 1:1. Other ratios include from 1,000,000:1 to 100,000:1; 100,000:1 to 50,000:1; 50,000:1 to 25,000:1; 25,000:1 to 15, 000:1; 15, 000:1 to 12, 000:1, 12, 000:1 to 11. 000:1, 11, 000:1 to 10, 000:1, 9, 000:1, 8, 000:1. 7, 000:1, 6, 000;1, 5, 000:1, 4, 000:1, 1, 000:1, 900:1, 500:1, 300:1, 200:1, 150:1, 100:1, 90:1, 80:1, 75:1, 70:1, 60:1, 50:1, 40:1, 30:1, 20:1, 10:1, 5:1 to 3:1, or interval ratio contained therein (e.g. 50:1 to 30:1 ) and also 1:1 to 1:20, or any other ratio that maximizes vapor phase combustion.
Every concentration which maximizes vapor phase combustion is contempated in the claims hereto.
Metallic salts may be employed in fuels at 0.01 to 4000.0 parts metallic to per million fuel, 1.0 to 150 ppm metallic being contemplated, with concentrations equal or less than 50.0, 40.0, 30.0, 20.0, 16.0, 10.0, 5.0 ppm metallic also contemplated. Other salt concentrations will vary from 0.10 to 75.0 ppm metal per million, from 30.0 to 2000.0 per million, from 25 to 750 parts metallic or salt per million fuel. In the application of Applicant's invention elemental metal concentrations from 3.0 to 500.0 ppm metal are expressly contemplated and desirable. Concentrations outside these ranges are contemplated.
It has been found that higher oxygen weight concentrations in fuel compositions, particularly with higher concentrations of enhanced combustion 2o properties, permit higher acceptable metallic concentrations. Higher average fuel densities are also associated with higher acceptable metallic concentrations and higher exhaust velocities, and are preferred. Engine combustion thermal dynamics and stoichiometry dictate upper metallic limits.
As noted above, elemental metallic concentrations will vary substantially. Non-limiting examples include elemental metallic concentrations equal to or greater than 1164, 1132, 1116, 3/32, 118, 5132, 3116, 114, 5116, 318, 7116, 1/2, 518, 314, 718, 1, 1.25, 1.5, 1.75, 2.0, 2.25, 2.5, 2.75, 3.0, 3.25, 3.5, 3.75, 4.0, 4.5, 5.0, 5.5, 6.0, 6.5, 7.0, 7.5, 8.0, 8.5, 9.0, 9.5, 10.0 gramslgal. In advance aviation, rocket andlor propellant and other 3 o applications, elemental metal concentrations can be on the order of 10 to 25, 20 to 40, 20 to 50, 20 to 100, even 50 to 1000, or more, gramslgal, especially in hypergolic conditions. Concentrations both above and below these ranges are contemplated. A11 combustion improving or stoichiometric amounts of elemental metal are contemplated, which maximize combustion so long as the resultant fuel's burning velocity increases compared to fuel absent metallic.
Thus, those metallic concentrations that maximize combustion velocity andlor other objects of this invention are expressly contemplated. Ranges will vary depending upon the specific metallic, its concentration, concentration and type of ECS oxygenates, the concentration and nature of hydrocarbon fuel composition, including its density, the intended application, relevant thermodynamics, extent combustion systems are modified to enhance the accelerated low temperature high energy nature of Applicant's invention, environmental regulation, and the like.
Metallics used in the fuel compositions of the present invention should be fuel soluble generally having melting and boiling ranges compatible with liquid hydrocarbons, or be incorporated into liquid fuel systems by means of 1o mutual solvents, dispersants, or other means, as required. Alternatively, the metallics may be introduced into the combustorlcombustion chamber of liquide or gaseous fuels (e.g. natural gas) by separate means, including separate injection, liquidification or gasification, colloidal media, suspension media. Metallics may be introduced into the combustor in an atomized, vaporized, or gasified form, separately andlor in combination with the other ingredients of the invention.
In solid fuel applications, the metallic may be introduced as a solid. In hybrid applications, it may be introduced as either as solid, liquid or gas, together with the balance of the invention's ingredients. Most preferably, the 2 o metallic is employed as a propellant or co-propellant, or jointly together with a propellant. Hydrogen content of the metallic andlor metallic containing fuel should be maximized, to the extent possible.
Those skilled in the art will appreciate that many variations and modifications of the invention disclosed herein may be made without 2 5 departing from the spirit and scope thereof.

Claims

1. A luminous combustion composition comprising:
I) a combustion improving amount of at least one ECS compound, said compound characterized as reducing combustion temperature and/or increasing burning velocity, having a minimum latent heat of evaporation of 21 kJ mol-1 at its boiling temperature, and a minimum burning rate (as measured by laminar Bunsen flame) of 40 cm/sec, said compound optionally selected from the group consisting of alcohols, aldehydes, amines, carbonic esters, carboxylic acids, carbonates, di-carbonates, esters, di-esters, ethers, di-ethers, glycols, glycol ethers, ketones, nitrates, di-nitrates, peroxides, hydroperoxides, phenols, said compound optionally containing at least one alkyl, alkyloxy, dialkyl, dialkyloxy, polyalkyl, polyalkyloxy, aryl, amide, acetate, aldehyde, carbethoxy, carbomethoxy, carbonyl, carbonyldioxy, carboxy, ethoxalyl, ethoxy, formyl, glycolyl, glyoxylyl, hydroxyl, imide, methoxy, methylenedioxy or nitrosyl radical, including derivatives, analogues, and homologues, and mixture;
II) a combustion improving amount of at least one non-leaded element or derivative organic or inorganic compound containing said non-lead element, selected from the group consisting of 1A, 2A, 3B, 4B, 5B, 6B, 7B, 8, 1B, 2B, 3A, 4A, 5A, 6A, or 7A elements of the Periodic Chart of Elements (CAS version), and mixture, wherein said element or derivative compound, is combustible and optionally has a minimum heating value of 4,000 Kcal/kg;
III) a combustion co-catalyst; optionally a:
IV) stabilizer, V) a co-fuel and/or oxidizer;
VI) wherein a luminous reaction zone extends from the surface of said non-lead element or derivative compound in combustion, optionally, where resultant oxides of said non-lead element are formed in the submicron range;
and VII) wherein said composition has a thermal efficiency of at least 2%
greater than unadjusted co-fuel (if any).

2. A fuel composition comprising: I) an combustible improving amount of an ECS oxygenate capable of increasing burning velocity and/or reducing combustion temperature, and II) a combustion improving amount of at least one combustible element or compound containing at least one element selected from the group consisting of aluminum, boron, bromine, bismuth, beryllium, calcium, cesium, chromium, cobalt, copper, francium, gallium, germanium, iodine, iron, indium, lithium, magnesium, manganese, molybdenum, nickel, niobium, phosphorus, potassium, palladium, rubidium, sodium, tin, zinc, praseodymium, rhenium, silicon, vanadium, strontium, barium, radium, scandium, yttrium, lanthanum, actinium, cerium, thorium, titanium, zirconium, hafium, praseodymium, protactinium, tantalum, neodyium, uranium, tungsten, promethium, neptunium, samarium, plutonium, ruthenium, osmium, europium, americium, rhodium, iridium, gadolinium, curium, platinum, terbium, berkelium, silver, gold, dysprosium, californium, cadmium, mercury, holmium, titanium, erbium, thulium, arsenic, antimony, ytterbium, selenium, tellurium, polonium, lutetium, astatine, mixture thereof, including organic and inorganic derivatives; and III) a co-combustion catalyst; said composition optionally having:
IV) a hydrogen or hydrocarbon base fuel, V) an oxidizer, VI) a pH of from 4.5 to 10.5; and wherein VII) said fuel is a vapor phase composition characterized upon combustion as having a luminous reaction zone extending from surface of said element.

3. The fuel composition of claim 1-2, wherein the ECS oxygenate is selected from the group consisting of methyl tertiary butyl ethers, ethyl tertiary butyl ether, tertiary methyl amyl ether, tertiary methyl ethyl ether, ethyl tertiary amyl ether, C1 to C6 aliphatic alcohols, dimethyl carbonate, diethyl carbonate, methylal, ethylal, and mixture.

4. The fuel composition of claim 1-2, wherein the co-combustion catalyst is selected from the group consisting of trimethoximethylsilane, ethoxytrimethylsilane, isobutyltriethoxy-silane, tetramethylsilane, dimethoxy-methyl-vinyl-silane, methyltriethoxysilane, 3-aminopropyl-triethoxysilane, 3-aminopropyl-trimethoxysilane, vinyltrimethoxysilane, diethoxydi-methylsilane, dimethoxydimethylsilane, vinyltris(2-butyldenamino-oxy)silane, tetraalkyloxysilanes, tetramethoxysilane, tetraethoxysilane, tetrapropyloxysilane, tetraisopropylsilane, tetraisobutylsilane, dialkylphosphites (e.g. dimethyl-phosphate, diethylphosphite, dipropylphosphite, dibutylphosphite, di-tert-butylphosphite, trialkylphosphites, trimethylphosphite, triethylphosphite, tripropylphosphite, triisopropylphosphite, tributylphosphite), dimethylmethylphos-phonate, diethylmethyl-phosphonate, P-pyrophosphate, trimethyl-orthoacetate, trimethylorthovalerate, trimethylorthobutyrate, trimethylortho-formate, alkyloxymethanes, tetraalkyloxymethanes, tetramethoxymethane, tetraethoxymethane, tetrapropoxymethane, tetraisopropoxy-methane, tetratert-butoxy-methane, potassium pryophosphite, trimethylorthoacetate, triethylorthoacetate, trimethylortho-butyrate, triethylortho-butyrate, trimethylorthovalerate, trimethylorthoformate, dimethoxymethane, diethoxyethane, tetra-methoxymethane, triethoxymethylmethane, tri-methoxymethylmethane, tetraethoxymethane, trimethoxymethylethane, triethoxymethylethane, glacial acetic acid, acetic acids anhydride, (acetyloxy) acid acid, ethyl ester (acetyloxy) acetic acid, aminooxo acetic acid, aminooxo acetic acid hydrazide, ammonium acetate, acetoacetic acid, methoxyacetic acid, ethoxyacetic acid, methoxy ethyl ester of acetic acid, methoxy methyl ester of acetic acid, ethoxy methyl ester of acetic acid, ethoxy ethyl ester of acetic acid, propoxy methyl ester of acetic acid, oxoacetic acid, alkylhydroxyesters of acetic acid, methylesterhydro-xyacetic acid, ethylesterhydroxy-acetic acid, propylesterhydro xyacetic acid, alkyl acetates, methyl ester acetic acid, ethyl arsenate, ethyl arsenite, methyl ester of butanic acid, ethyl ester of butanic acid, 2-hydroxybutanic acid, 3-hydroxybutanic acid, 3-hydroxy-ethylester of butanic acid, 2-hydroxyethylester of butanic acid, diphenyl carbonate, dipropyl carbonate, ethylmethyl carbonate, dibutyl carbonate, tetranitromethane, triethylphosphine oxide, triethylphosphine oxide, triethylphosphine, diethylphosphinic acid, dimethylphosphinic acid, ethyl diethylphosphinic acid, diethylphosphonic chloride, dibutyl ester phosphoric acid, (1,1-dimethylethyl) phosphoric acid, ethenyl diethyl ester phosphoric acid, diethyl ethyl-phosphonate, ethyl dimethylester phosphoric acid, methyl dimethylester phosphoric acid, methyl monoethylester phosphoric acid, methyl monomethylester phosphoric acid, methyl-O,O-dimethylester phosphonothioic acid, diethyl ester phosphoric acid, dimethyl ester phosphoric acid, tributyl phosphate, ethylphosphate, trimethyl ester ester phosphoric acid, triethyl ester ester phosphoric acid, tripropyl phosphate, O,O,O,-methyl ester phosphorothioic acid, diethylester phosphorous acid, dimethyfester phosphorous acid, tributyl ester phosphorous acid, triphenyl ester phosphorous acid, O,O,S-tiethyl ester phosphorodithioic acid, 2-methyl-1,2,propanediol, 2-methyl-2-nitro-1,3,-propanediol, 2-methyl-2-propyl-1,3,-propanediol, 1-nitrate-1,2, propanediol, 1,1',1",1'''-[methanetetrayltetrakis(oxy)]-tetrakis propane, methyl propyl ether, isopropylmethyl ether, isobutyl methyl ether, ethyl propyl ether, propylmethyl ether, butyl methyl ether, 1,1'-[methylenebis(oxy)]bis[2-methyl-propane, 1-(1-methylethoxy)-propane, 2,2',2"-[methylidyne-tris(oxy)]tris propane, 1,1',1"-[methylidynetris(oxy)]tris[2-methyl propane, 2-methyl-1-nitro propane, 2-methyl-2-nitro propane, hydracrylonitrile, 1,1,1-triethoxy-propane, 1,1,3-triethoxy-propane, 1,1,1-trimethoxy-propane, 1,1,3-trimethoxy-propane, 1,1,1-trifluoro-3-nitro-propane, 2-pyrrolidinone, phenol, and mixture.

5. The composition of claim 1-2, wherein the a co-combustion catalyst is selected from group consisting of trimethoxymethylsilane, ethoxytrimethylsilane, isobutyltriethoxysilane, tetramethylsilane, dimethoxy-methyl-vinyl-silane, methyltriethoxysilane, 3-aminopropyl-triethoxysilane, 3-aminopropyl-trimethoxysilane, vinyltrimethoxysilane, diethoxydimethylsilane, dimethoxydimethylsiiane, vinyltris(2-butyldenaminooxy)silane, tetramethoxysilane, tetraethoxysilane, tetrapropyloxysilane, tetraisopropylsilane, tetraisobutylsilane, dimethylphosphite, dipropylphosphite, diethylphosphite, dibutylphosphite, di-tert-butylphosphite, trialkylphosphites trimethylphosphite, triethylphosphite, triisopropylphosphite, tributylphosphite), dimethylmethylphosphonate, diethylmethylphosphonate, potassium pryophosphite, trimethylorthoacetate, triethylorthoacetate, trimethylorthobutyrate, triethylorthobutyrate, trimethylorthovalerate, trimethylorthoformate, including homolgues, analogues, isomers, derivatives, and mixture thereof.

6. The fuel composition of claim 1-2, wherein the co-combustion catalyst is selected from group consisting of trimethoxymethylsilane, dimethylphosphite, diethyphosphite, tetramethoxymethane, tetraethoxymethane, trimethoxymethylmethane, triethoxymethylmethane, methoxy methyl ester of acetic acid, tetranitromethane, and mixture.

7. The fuel composition of claim 1-6, wherein said ECS compound contains dimethyl carbonate, and said composition has a pH from 6.2 to 7.6.

8. The fuel composition containing an ECS oxygenate increasing burning velocity and/or reducing combustion temperature, optionally selected from MTBE, ETBE, DMC, DEC, methylal, ethylal, methanol, ethanol, or mixture, and a metal selected from [2-(cyclohexenyl)ethyl]triethoxysilane, cyclohexenyl dimethoxymethylsilane, benzyltrimethylsilane, N-(3-(trimethoxysilyl)propyl)ethylenediamine, N-1-(3-(trimethoxysilyl)propyl)diethylenetriamine, N-(3-(trimethoxysilyl)propyl)ethylenediamine, 1-(trimethyl(silyl)pynolidine, triphenylsilanol, octamethyltrisiloxane, 2,2,4,4,6,6-hexamethylcyclotrisilazane, hexamethylcyctrisiloxane, hexamethyldisilane, 1,1,1,3,3,3-hexamethyl disilazane, hexamethyldisiloxane, hexamethyldisilthiane, allyltributylsilane, tetraalkylsilanes (e.g. tetraethylsilane, tetrabutylsilane, etc.), 3-aminopropyltriethoxysilane, benzytrimethylsilane, benzytriethylsilane, N-benzyltrimethylsilylamine, diphenylsilanediol, dihexylsilanediol, (trimethylsilyl)cyclopentadiene, potassium methoxide, potassium ethoxide, potassium propoxide, potassium isopropoxide, potassium butoxide, potassium sec-butoxide, potassium tert-butoxide, potassium pentoxide, potassium tert-pentoxide, potassium phenoxide, potassium salt of acetic acid, potassium hydrogenphthalate, potassium hydrogensulfate, monopotassium acetylenedicarboxylic acid, potassium pyrophosphate, potassium dihydrogenphosphate, potassium benzoate, potassium chloride, potassium hexoate (potassium salt hexoic acid), potassium acetate, potassium diphenylphosphide, potassium trimethylsilonalate, potassium phthalic acid, P-aminobenzoic acid potassium salt, monopotassium L-aspartic acid, potassium napthenate, potassium hexacyanoferrate (II), potassium hexacyanoferrate (III), potassium hexacyanocobalt II- ferrate, potassium hexacyanocobalt, potassium sodium ferricyanide, or mixture.

9. The composition of claim 1-8, being an enhanced aviation turbine fuel composition wherein aviation turbine hydrocarbon base has a viscosity equal or exceeding 8.1 MM2/S, a C3 to C7 symmetrical dialkyl dicarbonate, said fuel optionally characterized as being slightly acidic not exceeding equivalent of 0.1 mg KOH/g.

10. The composition of claim 1-8, wherein the fuel composition is a diesel fuel oil, the ECS oxygenate is dimethyl carbonate representing 0.01% to 40.0% oxygen by wt. of the fuel, the hydrocarbon base fuel has a viscosity equal to or greater than 2.5, MM2/S at 40°C, and the fuel composition is characterized as having a pH less than 10.5 and a viscosity equal to or less than 2.4 MM2/S at 40°C.

11. A fuel composition of claim 1-8, wherein said composition is a gasoline comprising an ECS oxygenate selected from MTBE, ETBE, DMC, or ethanol, characterized as having a pH ranging form 8.5 to 5.5, optionally a maximum Reid Vapor Pressure of 12.0 psi or 8.0 psi, a maximum of 12% vol. olefins, a maximum of 30% vol. aromatics, a maximum of 1.0% vol, benzene, a maximum of 50 ppm sulfur or sulfur free, a total O2 concentration ranging from 0.5% to 4.0% wt of the composition, a maximum T-90 temperature of 330°F to 280°F, a T-50 temperature of approx. 170°F to 230°F., a minimum (R+M)/2 octane of 85, to 92, a bromine number of 20 or less, an average latent heat of vaporization of 880 to 920 BTU/gal at 60°F, a heating value greater than 106,000 btu/gal at 60°F.

12. A fuel composition comprising:
I) a hydrocarbon fuel base, and II) a co-combustion agent selected from the group consisting of trimethoxymethylsilane, ethoxytrimethylsilane, isobutyltriethoxysilane, tetramethylsilane, dimethoxy-methyl-vinyl-silane, methyltriethoxysilane, 3-aminopropyl-triethoxysilane, 3-aminopropyl-trimethoxysilane, vinyltrimethoxysilane, diethoxydimethylsilane, dimethoxydimethylsilane, vinyltris(2-butyldenaminooxy)silane, tetramethoxysilane, tetraethoxysilane, tetrapropyloxysilane, tetraisopropylsilane, tetraisobutylsilane, dimethylphosphite, dipropylphosphite, diethylphosphite, dibutylphosphite, di-tert-butylphosphite, trialkylphosphites trimethylphosphite, triethylphosphite, triisopropylphosphite, tributylphosphite), dimethylmethylphosphonate, diethylmethylphosphonate, potassium pryophosphite, trimethylorthoacetate, triethylorthoacetate, trimethylorthobutyrate, triethylorthobutyrate, trimethylorthovalerate, trimethylorthoformate, including homolgues, analogues, isomers, derivatives, and mixture thereof; optionally an ECS
compound.

13. A fuel composition comprising: a hydrocarbon base; a combustion improving amount of an ECS metal is a combustible compound is selected from [2-(cyclohexenyl)ethyl]triethoxysilane, cyclohexenyl dimethoxymethylsilane, benzyltrimethylsilane, N-(3-(trimethoxysilyl) propyl)ethylenediamine, N-1-(3-(trimethoxysilyl)propyl)diethylenetriamine, N-(3-(trimethoxysilyl)propyl)ethylenediamine, 1-(trimethyl(silyl)pyrrolidine, triphenylsilanol, octamethyltrisiloxane, 2,2,4,4,6,6-hexamethylcyclotrisilazane, hexamethylcyctrisiloxane, hexamethyldisilane, 1,1,1,3,3,3-hexamethyl disilazane, hexamethyldisiloxane, hexamethyldisilthiane, allyltributylsilane, tetraalkylsilanes (e.g. tetraethylsilane, tetrabutylsilane, etc.), 3-aminopropyltriethoxysilane, benzytrimethylsilane, benzytriethylsilane, N-benzyltrimethylsilylamine, diphenylsilanediol, dihexylsilanediol, (trimethylsilyl)cyclopentadiene, potassium methoxide, potassium ethoxide, potassium propoxide, potassium isopropoxide, potassium butoxide, potassium sec-butoxide, potassium tert-butoxide, potassium pentoxide, potassium tert-pentoxide, potassium phenoxide, potassium salt of acetic acid, potassium hydrogenphthalate, potassium hydrogensulfate, monopotassium acetylenedicarboxylic acid, potassium pyrophosphate, potassium dihydrogenphosphate, potassium benzoate, potassium chloride, potassium hexoate (potassium salt hexoic acid), potassium acetate, potassium diphenylphosphide, potassium trimethylsilonalate, potassium phthalic acid, P-aminobenzoic acid potassium salt, monopotassium L-aspartic acid, potassium napthenate, potassium hexacyanoferrate (II), potassium hexacyanoferrate (III), potassium hexacyanocobalt II- ferrate, potassium hexacyanocobalt, potassium sodium ferricyanide, or mixture; optionally an ECS oxygenate and/or a co-combustion catalyst.

14. A fuel composition comprising:
I) an ECS oxygenate selected from the group consisting of C2 - C12 aldehydes, aldehydic acids, C2 -C12 ethers, ether acids, C1 - C15 alcohols, C2 - C12 oxides, C3 - C15 ketones, ketonic acids, C3 - C15 esters, othroesters, C3 - C12 diesters, C5 -C12 phenols, C3 - C20 glycol ethers, C2 - C12 glycols, C3 - C20 alkyl carbonates, C3 - C20 dialkyl carbonates, C3 - C20 asymmetrical alkyl carbonates, C3 - C20 di-carbonates, C1 to C20 organic and inorganic peroxides, hydroperoxides, carboxylic acids, amines, nitrates, di-nitrates, oxalates, phenols, glacial acetic acids, C3 to C8 hyrodoxy esters of acetic acid, methoxy methyl ester of acetic acid,acetic acid anhyrides, methoxy methyl ester of acetic acid, boric acids, orthoborates, hydroxyacids, orthoacids, anhydrides, acetates, acetyls, formic acids, nitrates, di-nitrates, nitro-ethers; and II) an ECS metallic selected from the group consisting of [2-(cyclohexenyl)ethyl]triethoxysilane, cyclohexenyl dimethoxymethylsilane, benzyltrimethylsilane, N-(3-(trimethoxysilyl)propyl)ethylenediamine, N-1-(3-(trimethoxysilyl)propyl)diethylenetriamine, N-(3-(trimethoxysilyl)propyl)ethylenediamine, 1-(trimethyl(silyl)pyrrolidine, triphenylsilanol, octamethyltrisiloxane, 2,2,4,4,6,6-hexamethylcyclotrisilazane, hexamethylcyctrisiloxane, hexamethyldisilane, 1,1,1,3,3,3-hexamethyl disilazane, hexamethyldisiloxane, hexamethyldisilthiane, allyltributylsilane, tetraalkylsilanes (e.g. tetraethylsilane, tetrabutylsilane, etc.), 3-aminopropyltriethoxysilane, benzytrimethylsilane, benzytriethylsilane, N-benzyltrimethylsilylamine, diphenylsilanediol, dihexylsilanediol, (trimethylsilyl)cyclopentadiene, potassium methoxide, potassium ethoxide, potassium propoxide, potassium isopropoxide, potassium butoxide, potassium sec-butoxide, potassium tert-butoxide, potassium pentoxide, potassium tert-pentoxide, potassium phenoxide, potassium salt of acetic acid, potassium hydrogenphthalate, potassium hydrogensulfate, monopotassium acetylenedicarboxylic acid, potassium pyrophosphate, potassium dihydrogenphosphate, potassium benzoate, potassium chloride, potassium hexoate (potassium salt hexoic acid), potassium acetate, potassium diphenylphosphide, potassium trimethylsilonalate, potassium phthalic acid, P-aminobenzoic acid potassium salt, monopotassium L-aspartic acid, potassium napthenate, potassium hexacyanoferrate (II), potassium hexacyanoferrate (III), potassium hexacyanocobalt II- ferrate, potassium hexacyanocobalt, potassium sodium ferricyanide, or mixture; and, III) optionally a co-combustion catalyst;
IV) optionally a hydrocarbon base;
V) optionally an oxider;
VI) optionally a stabilizer; and VII) wherein said fuel is a vapor phase composition characterized upon combustion as having a luminous reaction zone extending from surface of said element.

15. The compositions of claims 1-14, wherein the ECS compound is optionally selected from MTBE, ETBE, TAME, methanol, ethanol, DMC, DEC, or mixture, and said ESC metal is hexamethyldisilane.

16. The composition of claims 1-14, wherein the ECS compound is optionally selected from MTBE, ETBE, TAME, methanol, ethanol, DMC, DEC, or mixture, and contains at least one potassium derivative.

17. The composition of claim 16, wherein said potassium derivative is selected from potassium methoxide, potassium ethoxide, potassium propoxide, potassium butoxide, potassium tert-butoxide, potassium phenoxide, potassium acetate, and mixture.

18. The composition of claims 1-14, wherein the ECS compound is optionally selected from MTBE, ETBE, TAME, methanol, ethanol, DMC, DEC, or mixture, and said ECS metallic is [2-(cyclohexenyl)ethyl]-triethoxysilane.

19. The composition of 1-14, wherein the ECS compound is optionally selected from MTBE, ETBE, TAME, methanol, ethanol, DMC, DEC, or mixture, and said ECS metallic is potassium hexacyanoferrate (II), potassium hexacyanoferrate (III), potassium hexacyanocobalt II- ferrate, potassium hexacyanocobalt, potassium sodium ferricyanide, or mixture.

20. The composition of claims, 1-19, wherein the pH is substantially neutral.

21. The composition of claim 1-14, wherein the ECS metallic is selected from potassium ethoxide, [2-(cyclohexenyl)ethyl]triethoxysilane, potassium hexacyanoferrate (II), potassium hexacyanoferrate (III), potassium hexacyanocobalt II- ferrate, potassium hexacyanocobalt, potassium sodium ferricyanide, or mixture.

22. A gasoline composition comprising a combustible alkali/alkali earth metal, and an ECS oxygenate selected from MTBE, ETBE, ethanol, methanol, DMC, EMC, and mixture, and an automotive gasoline, wherein resultant composition has one or more of the following characteristics: a RVP of 6.4 to 10.0 psi, aromatics content of 0% to 50% vol., a benzene content of 0% to 2.0% vol., an olefin content of 0% to 25% vol., an distillation evaporation point where 30% to 70% of the fuel has distilled by 200°F, an distillation evaporation point where 70% to 100% of the fuel has distilled by 300°F, a co-combustion catalyst, oxygen by wt% ranging from 0.1 % to 4.0%, sulfur, ppm, wt. ranging from 0 to 500 ppm.

23. A gasoline composition of claim 22, wherein the metal is a fuel combustible potassium derivative and an oxygenate is selected from MTBE, ETBE, ethanol, DMC, EMC, and wherein the composition has a maximum RVP of 7.2 psi, maximum aromatics of 22% vol., max. benzene of 1.0% vol., a minimum T50 distillation temperature of 175°F and a maximum T50 distillation temperature ranging from 200°F to 220°F, maximum T90 distillation temperature of 290°F to 310°F, oxygen by wt% 1.8% to 2.2%., sulfur, ppm, wt. 30 to 80.

24. A fuel composition comprising: I) an ECS oxygenate in a combustion improving amount, and II) a combustion improving amount of a ferricyanide; and optionally:
III) a co-combustion catalyst, IV) hydrogen or a hydrocarbon base fuel, V) an oxidizer, VI) a solvent or blending agent, VII) a pH of from 4.5 to 10.5; and VIII) wherein said fuel is a vapor phase composition characterized upon combustion as having a luminous reaction zone extending from surface of said element.

25. The fuel composition of claim 24, wherein the ferricyanide is selected from potassium hexacyanoferrate (II) or (III), magnesium ferrocyanide, magnesium potassium ferrocyanide.

26. The fuel composition of claim 1-25, wherein an ECS oxygenated is employed selected from the group consisting of methyl tertiary butyl ethers (MTBE), ethyl tertiary butyl ether (ETBE), tertiary methyl amyl ether (TAME), tertiary methyl ethyl ether (TEME), ethyl tertiary amyl ether, C1 to C6 aliphatic alcohois, including but not limited to ethanol, methanol, lower diakyl carbonates, including dimethyl carbonate (DMC), diethyl carbonate (DEC);
ethers having dual linkage, including methyal (methylene di methyl ether or dimethoxy methane), ethylal (diethoxy methane); carbons having multiple alkyloxy groups, including tetramethoxymethane, anhydrides and hyrodoxy esters of acetic acid, including methoxy methyl ester of acetic acid, ethoxy methyl ester of acetic acid.

27. The composition of claims 1-26, contain a co-combustion agent selected from the group consisting of trimethoxymethylsilane, ethoxytrimethylsilane, isobutyltriethoxysilane, tetramethylsilane, dimethoxy-methyl-vinyl-silane, methyltriethoxysilane, 3-aminopropyl-triethoxysilane, 3-aminopropyl-trimethoxysilane, vinyltrimethoxysilane, diethoxydimethylsilane, dimethoxydi-methylsilane, vinyltris(2-butyldenaminooxy)silane, tetramethoxysilane, tetraethoxysilane, tetrapropyloxysilane, tetraisopropylsilane, tetraisobutylsilane, dimethylphosphite, dipropylphosphite, diethylphosphite, dibutylphosphite, di-tert-butylphosphite, trialkylphosphites trimethylphosphite, triethylphosphite, triisopropylphosphite, tributylphosphite), dimethylmethylphosphonate, diethylmethylphosphonate, potassium pryophosphite, trimethylorthoacetate, triethylorthoacetate, trimethylorthobutyrate, triethylorthobutyrate, trimethylorthovalerate, trimethylorthoformate, including homolgues, analogues, isomers, derivatives, and mixture thereof.

28. The composition of claims 1-22, containing a stabilizer, optionally being a glycol ether, aromatic hydrocarbon or mixture.

29. The composition of claims 1-23, additionally containing a nitrogen based enhancer, optionally being a phosphoramide.

30. The compositions of claims 1-29, additionally contain a cyclopentadienylmanganese tricarbonyl compound.

31. A method of minimizing hydrolysis of a fuel composition comprising the steps of:
providing a symmetrical lower dialkyl carbonate;
providing an combustion improving amount of at least one combustible compound containing at least one element selected from the group consisting of aluminum, boron, bromine, bismuth, beryllium, calcium, cesium, chromium, cobalt, copper, francium, gallium, germanium, iodine, iron, indium, lithium, magnesium, manganese, molybdenum, nickel, niobium, phosphorus, potassium, palladium, rubidium, sodium, tin, zinc, praseodymium, rhenium, silicon, vanadium, strontium, barium, radium, scandium, yttrium, lanthanum, actinium, cerium, thorium, titanium, zirconium, hafium, praseodymium, protactinium, tantalum, neodyium, uranium, tungsten, promethium, neptunium, samarium, plutonium, ruthenium, osmium, europium, americium, rhodium, iridium, gadolinium, curium, platinum, terbium, berkelium, silver, gold, dysprosium, californium, cadmium, mercury, holmium, titanium, erbium, thulium, arsenic, antimony, ytterbium, selenium, tellurium, polonium, lutetium, astatine, mixture thereof, including their organic and inorganic derivative compounds;
providing a hydrocarbon;
mixing said carbonate, said combustible compound, and said hydrocarbon so as to produce a fuel composition having a pH of from 4.5 to 9.5, and store said composition at a temperature of no more than 90°F for up to 6 months, or longer, and, combusting said fuel in an engine or combustor, wherein vapor phase composition occurs characterized as having a luminous reaction zone extends from surface of said element.

32. The method of claim 31, wherein said fuel is stored at an average temperature of 65EF for 6 months, prior to combustion.

33. A method of mitigating handling hazards of an alkali/alkali earth metal based vapor phase combustion fuel composition, comprising the steps of:
providing an combustion improving amount of a combustible compound containing at least one element selected from an alkali metal or alkali earth metal, and mixture; and a stabilizer.

34. The method of claim 33, optionally providing an acidic ECS metallic; and optionally providing a hydrocarbon; and optionally providing an ECS oxygenate; and mixing said composition.

35. The method of claim 33-34, wherein the composition's target pH ranges up to 9.5.

36. The method of 35, wherein the pH is ranges from 6.0 to 8Ø

37. The method of 35-36, wherein the target pH is acheived by providing at least one acidic ECS metallic or acidic ECS oxygenate.

38. A method of reducing green house nitrous oxide gases, said method comprising:
mixing a combustion improving amount of an ECS metallic, optionally a combustion improving amount of an ECS oxygenate, together with a gasoline;
and combusting said resultant fuel composition in an automotive engine;
and exhausting resultant emissions through an exhaust catalyst; and emitting catalyst reacted emissions into the atmosphere; whereby exhaust nitrous oxide emissions are reduced.

39. The method of claim 38, wherein the fuel composition comprises a combustible alkali/alkali earth metal, and an ECS oxygenate selected from MTBE, ETBE, ethanol, methanol, DMC, EMC, and mixture, having one or more of the following characteristics: a RVP of 6.4 to 10.0 psi, aromatics content of 0% to 50%, a benzene content of 0% to 2.0%, an olefin content of 0% to 25%, an distillation evaporation point where 30% to 70% of the fuel has distilled by 200°F, an distillation evaporation point where 70% to 100%
of the fuel has distilled by 300°F, a minimum T50 distillation temperature of 175°F
and a maximum T50 distillation temperature ranging from 200°F to 220°F, maximum T90 distillation temperature of 290°F to 310°F,a co-combustion catalyst, oxygen by wt% ranging from 0.1% to 4.0%, sulfur, ppm, wt. ranging from 0 to 500 ppm.

40. The method of claim 38-39, wherein the fuel composition contains a combustion catalyst.

41. The method of claim 38-40, wherein the fuel composition has a pH
ranging from 5.0 to 9Ø