US3887593A

US3887593A - Preparation of nitroketonized amides

Info

Publication number: US3887593A
Application number: US270362A
Authority: US
Inventors: Donald R Lachowicz; George S Saines; George W Eckert
Original assignee: Texaco Inc
Current assignee: Texaco Inc
Priority date: 1970-12-24
Filing date: 1972-07-10
Publication date: 1975-06-03
Anticipated expiration: 1992-06-03

Abstract

A method of preparing a nitroketonized amide by contacting an acid amide of the formula:

WHERE R1 is an alkenyl group of from 4 to 40 carbon atoms, where R2 and R3 alternately represent hydrogen and an alkenoyl group of from 4 to 40 carbon atoms, with dinitrogen tetroxide and oxygen, at mole ratios of acid amide to dinitrogen tetroxide to oxygen of from 1:2:2 to 1:4:60.

Description

United States Patent Lachowicz et al. June 3, 1975 [54] PREPARATION OF T ZED 3,746,729 7/1973 Lachowicz 260/4045 AMIDES P E L G rimary xaminer ewis otts [75] Inventors 3 5' fi gl if fr gg Assistant ExaminerEthel G. Love t a 1s Attorney, Agent, or FirmT. H. Whaley; C. G. Ries; appmgers a a 0 George J. Darsa [73] Assignee: Texaco Inc., New York, NY. [57]- ABSTRACT [22] Fil d; J l 10, 1972 A method of preparing a nitroketonized amide by con- [21] pp No: 270,362 tactlng an acid amide of the formula:

Related U.S. Application Data 1 N CH2 CH2 CH2 N H [62] Division of Ser. No. 101,408, Dec. 24, 1970, Pat. No. 2 3

[52] U.S. Cl 260/4045; 44/7]; 260/561 K; where R is an alkenyl group of from 4 to 40 carb 260/561 N atoms, where R and R alternately represent hydro- [51] Int. Cl. C07c 103/30 g n n n alkenoyl group of from 4 to 40 carbon [58] Field of Search 260/4045, 561 K atoms, i h n rog n etroxide and oxygen, at mole ratios of acid amide to dinitrogen tetroxide to oxygen References Cited of from 1:222 to 1:4:60.

UNITED STATES PATENTS 8 Claims, No Drawings 3,458,582 7/1969 Lachowicz et al 260/4045 X 1 PREPARATION OF NITROKETONIZED AMIDES This is a division of application Ser. No. 101,408, filed Dec. 24, 1970, now US. Pat. No. 3,711,255.

BACKGROUND OF THE INVENTION This invention relates to an improved motor fuel composition for internal combustion engines. More particularly, the invention involves the discovery that the incorporation of a minor amount of a nitroketonized amide into gasoline produces a fuel having improved carburetor detergent properties along with good corrosion inhibiting and anti-icing properties.

Modern internal combustion engine design is undergoing significant changes to meet higher standards concerning engine and exhaust gas emissions. A major change in engine design presently being widely adopted is the feeding of crankcase blow-by gases of the engine into the intake air supply to the carburetor rather than venting to the atmosphere as was done in the past. Blow-by gases, however, contain substantial amounts of deposit-forming substances and it has been observed that some of the constituents in the blow-by gas form deposits in and around the throttle plate area of the carburetor. Such deposits restrict the flow of air through the carburetor at idle and low speeds resulting in an overrich fuel mixture. Such a condition produces rough idling, engine stalling and also results in excessive hydrocarbon exhaust emissions to the atmosphere. In addition to overcoming the foregoing problem, a competitive modern gasoline must provide a high degree of corrosion inhibiting and anti-icing properties.

A novel fuel composition has been discovered which mitigates or overcomes the problem of deposit laydown in the carburetor of an internal combustion engine. More specifically, a motor fuel composition containing a novel additive has been found which is effective for substantially reducing the laydown of deposits in a carburetor. The additive also provides excellent corrosion inhibiting and anti-icing properties in the gasoline.

Broadly, this invention contemplates a motor fuel composition comprising a mixture of hydrocarbons in the gasoline boiling range and a minor amount of a nitroketonized amide corresponding to the formula:

R Ill CH -Ch CH where R is an alkyl, alkenyl, nitroketonized alkyl or nitroketonized alkenyl group, where R and R alternately represent hydrogen and an alkanoyl, alkenoyl, nitroketonized alkanoyl or nitroketonized alkenoyl group, wherein at least one of said R, R or R" is a nitroketonized group as heretofore defined. In particular, R when alkyl represents a group having from 1 to 40, preferably 8 to 22, carbon atoms and when alkenyl, nitroketonized alkyl or nitroketonized alkenyl represents a group having from 4 to 40, preferably 8 to 22, carbon atoms. Further, R and R when alternately representing a group recited above, other than hydrogen, contains from 4 to 40, preferably 8 to 22, carbon atoms. The nitroketonized amides employed in this invention are prepared by contacting the precursor, namely an acid amide, of the formula:

where R is an alkyl group having from 1 to 40 carbon atoms or alkenyl group having from 4 to 40 carbon atoms, where R and R alternately represent hydrogen and an alkanoyl group or an alkenoyl group having from 4 to 40 carbonatoms, wherein at least one of said R, R orR is analkenyl or an alkenoyl group, with dinitrogen tetroxide and oxygen at a temperature of from about 35 to 45C. in a mole ratio of said acid amide to dinitrogen tetroxide to oxygen of from 1:1:1 and 1:4:60. In a desirable embodiment R and R or R are respectively alkenyl and alkenoyl groups having from 4 to 40, preferably 8 to 22, carbon atoms and where the mole ratio of acid amide to dinitrogen tetroxide to oxygen is from 1:22 to 1:4:60. Preferably, the reaction is conducted at temperatures of from 10 to 30C. and R, R or R represent groups having from 8 to 22 carbon atoms.

Nitroketonization of the afroementioned acid amide can be accomplished in a one-step reaction as contrasted to other known processes where olefins are initially converted to intermediate nitroperoxy compounds and where the intermediate compound is subsequently contacted with a denitrating agent to yield a nitroketone product. Here, the introduction of a denitrating agent is not essential inasmuch as autogenous conversion at the point of unsaturation directly results in vicinal nitroketonization.

The acid amide containing at least one group identified as R, R or R possessing at least one unsaturated (-Cl-l CH) group along a carbon chain is converted in the course of nitroketonization to a vicinal nitroketone function N02 0 l 11 (-CH c For example, unsaturation of the acid amide may be in R as an alkenyl group such as 3-buteny1, Z-pentenyl, lO-undecenyl, 9-octadecenyl and 13-docosenyl. Alternatively R may be an alkyl group such as methyl, ethyl, butyl, hexyl, dodecyl, hexadecyl and tetracosanyl. When R is alkyl unsaturation of the acid amide occurs at R or R as an alkenoyl group such as 2-methyl-3- butenoyl, 3-butenoyl, l0 undecenoyl, 8-hexadecenoyl, 9-octadecenoy1 and l3-docosenoy1. Alternatively when R or R is alkanoyl, such as isobutanoyl, heptanoyl, decanoyl, pentadecanoyl and tetracosanoyl, R is an alkenyl group. Further, unsaturation may occur in a plurality of points along R, R or R Moreover, unsaturation at one or more points may occur simultaneously in R and R or R as when R is 9-octadecenyl and R or R is 10-undecenoyl. Depending on the ratio of acid amide to dinitrogen tetroxide to oxygen, acid amides having a plurality of unsaturated linkages can to varying degrees be singularly to totally converted to vicinal nitroketone groups. Where a plurality of unsaturation occurs and it is contemplated that some or all be converted to vicinal nitroketone groups the lower ratios of acid amide to dinitrogen tetroxide to oxygen of 1:212 to 124260 are employed along with a denitrating agent introduced to the reaction product resulting from contacting of the acid amide, dinitrogen tetroxide and oxygen.

The denitrating agent is added to the reaction product in a mole ratio of agent to product of at least 1:1 and preferably less than about 20:1 at a temperature about 35 to 45C. Specific examples of denitrating agents include dimethylformamide, diethylformamide, dimethylacetamide, dimethylsulfoxide, diethylsulfoxide, tetramethylurea and tetraethylurea.

When unsaturation of R R or R occurs internally, that is, on other than a terminal carbon atom, the reaction yields a mixture of two isomeric vicinal nitroketonized amides, illustratively, N-( 9-nitrol octadecanonyl)-N '-octadecanoyll ,3-diaminopropane and N-( l0-nitro-9-octadecanonyl)-N'-octadecanoyl- 1,3-diaminopropane. When unsaturation occurs be tween the terminal and adjacent carbon atom, nitration occurs on the terminal carbon and ketonization on the carbon vicinal thereto as for example N-decyl-N-(4- nitro-3-butanonyl)1 ,3-diaminopropane.

The unsaturated acid amide employed as a starting reactant is prepared from readily available materials. Essentially, such an acid amide is provided by reacting primary amine with acrylonitrile to yield the corresponding N-( 2-cyanoethyl-N-alkylamine and subsequently selectively hydrogenating the cyano group to the N-hydrocarbyl-l,3-diaminopropane (a diamine) where the hydrocarbyl radical is alkyl or alkenyl. Subsequently, the N-hydrocarbyl-l ,3-diaminopropane is reacted with a C to C alkanoic or alkenoic acid to form an ammonium salt of the acid which upon heating in the absence of added water is converted to the acid amide. With regard to the alkenyl or alkenoyl group, each may have one or more points of unsaturation that subsequently undergo nitrokentonization according to the process herein described. For example, polyunsaturated acids as those occurring in whale oil, fish oil, corn oil, linseed oil and other oils can be employed including 9,12-octadecadienoic acid and 9,12,15- octadecatrienoic acid.

In the course of nitroketonization of the acid amide, air can be employed as the source of oxygen or oxygen can be provided in admixture with inert gases such as nitrogen or argon. Under preferred conditions, oxygen and dinitrogen tetroxide are respectively introduced into the reaction zone containing the amide at a rate of between 1 and 16 milliliters per minute of oxygen per gram of amide and between about 0.005 and 0.05 grams of dinitrogen tetroxide per minute per gram of amide. Atmospheric and higher pressures may be employed and the reaction is conveniently conducted in the presence of inert organic solvents having from 4 to 22 carbon atoms exemplified by hydrocarbons including paraffins such as pentane, hexane, octane, decane, dodecane, octadecane; cycloparaffins such as cyclopentane and cyclohexane; and aromatic hydrocarbons such as benzene and toluene. In general, reaction times of about one-half to ten hours are employed, the time related to the rate of addition of the dinitrogen tetroxide.

It is to be noted that the dinitrogen tetroxide employed is actually an equilibrium mixture of dinitrogen tetroxide and nitrogen dioxide with the equilibrium being driven to essentially 100 percent dinitrogen tetroxide at 0C. and essentially 100 percent nitrogen dioxide at 140C. at 1 atmosphere pressure.

Nitroketonized amides contemplated as motor fuel additives herein include by way of illustration and not limitation N-hexyl-N'-(9-nitro-l0-octadecanonoyl)-1,3-

diaminopropane,

N-hexyl-N-( l0-nitro-9-octadecanonoyl)-l ,3-

diaminopropane,

N-hexyl-N-(9-nitrol 0-octadecanonoyl l ,3-

diaminopropane,

N-hexyl-N-(10-nitro-9-octadecanonoyl)-l,3-

diaminopropane,

N-(9-nitrol 0-octadecanonyl )-N'-heptanoyll ,3-

diaminopropane,

N-( 10-nitro-9-octadecanonyl)-N-heptanoyl-l ,3-

diaminopropane,

N-( 13-nitro-l4-docosanonyl)-N'-(8-hexadecenoyl)- l ,3-diaminopropane,

N-( l4-nitro- 1 3-docosanonyl)-N 8-hexadecenoyl)- 1 ,3-diaminopropane,

N-( l3-docosenyl)-N'-(8-nitro-9-hexadecanonoyl)-l ,3-

diaminopropane,

N-( l 3-docosenyl)-N-(9-nitro-8-hexadecanonoyl)-l ,3-

diaminopropane,

N-(13-nitro-l4-docosanonyl)-N'-(8-nitro-9- hexadecanonoyl)-l ,3-diaminopropane and N-( 14- nitro-l 3-docosanonoyl )-N-( 8-nitro-9- hexadecanonoyl)-l ,S-diaminopropane.

In general, effective detergent motor fuels are produced by adding from about 0.0001 to 0.1 weight percent of the nitroketonized amide to the gasoline. A preferred concentration of the nitroketonized amide is in the range from about 0.001 to 0.02 weight percent which corresponds to about 3 to 60 PTB (pounds of additive per 1000 barrels of fuel).

The carburetor detergency effect of the additive and motor fuels containing the same was determined in a specially developed engine test designated the Chevrolet V-8 Carburetor Detergency Test. This test was conducted using a Chevrolet V-8 engine equipped with a 4-barrel carburetor mounted on a test stand. The two secondary barrels of the carburetor were sealed and each of the primary barrels arranged so that an additive fuel could be run in one barrel and a base fuel run in the other. The primary carburetor barrels were modified to the extent that they had removable aluminum inserts in the throttle plate area so that deposits formed in this area could be conveniently weighed.

In the test designed to determine the effectiveness of the detergent-containing fuel for preventing the laydown of deposits, the engine is run for a period of 24 to 48 hours with the base fuel being fed to one barrel and the additive fuel to the other barrel while engine blow-by is circulated to the air inlet of the carburetor. After the run, the inserts are removed from the carburetor and weighed to determine the difference between the performance of the additive and non-additive fuels. The aluminum inserts are then cleaned, replaced in the carburetor and the process repeated with the fuels reversed in the carburetor barrels to minimize differences in fuel distribution and barrel construction. The deposit weights in the two runs are averaged and the detergency effectiveness of the additive fuel expressed in percent.

The anti-icing properties of the additive-containing fuel of the invention was determined in a carburetor icing demonstrator apparatus consisting of a vacuum pump equipped so that cool moisture-saturated air from an ice tower is drawn through a sample glass tube gasoline carburetor. The gasoline sample is placed in a sample bottle and is drawn into the glass carburetor Y 1 through a 20 gage hypodermic needle. Evaporation of the gasoline in the gas tube further cools the cold moist air with resulting ice formation on the throttle plate. The formation of ice on the throttle plate causes an engine to stall and it has been found that this condition is equivalent to a pressure drop across the throttle plate of about 0.5 inches and 0.9 inches of mercury and the time required to reach this pressure drop is noted. The vacuum pump is adjusted to give a vacuum of 1.8 inches of mercury and the test is run until either a pressure of 2.3 inches mercury has been reached or the run has continued for 300 seconds. Since, with most fuels, this pressure drop is reached in l to 4 minutes 300 seconds is the maximum time for a run. A fuel composition which provides a minimum of 200 seconds run in'this test is an effective carburetor anti-icing fuel composition.

The anti-rusting properties of motor fuels was determined by inserting and thoroughly wetting a cold-rolled steel strip into a tall form four ounce glass bottle containing 90 cc of the fuel sample and adding 20 cc of distilled water. The bottle was stoppered, agitated for 15 seconds and stored at room temperature for 24 hours. The strip was thereafter visually inspected and the percentage of rusted surface area estimated.

In order to more fully illustrate the nature of this invention and manner of practicing the same, the following examples are presented.

EXAMPLE I To a solution of 14.7 grams (0.025 mole) of a mixture of N-(9-octadecenyl)-N-(9-octadecenoyl)-1,3- diaminopropane and N-(9-octadecenyl)-N-(9- octadecenoyl)-l,3-diaminopropane in 200 ml. of nhexane as inert solvent, there was added simultaneously oxygen at a rate of 60.8 milliliters per minute and dinitrogen tetroxide at the rate of 0.0081 moles per hour for 3.1 hours at 0C. After 3.1 hours, 1.5 milliliters of liquid dinitrogen tetroxide (0.025 mole) has been transferred to the reaction flask and the solution was purged with oxygen for about 1 hour. The reaction mixture was washed with 150 ml. of 3.3% aqueous sodium bicarbonate and twice with 100 milliliters of water and dried over sodium sulfate. Sodium sulfate was subsequently removed by filtration and the nhexane was stripped by rotary evaporation leaving a product residue of 10.8 grams. Infrared spectroscopic analysis of the product obtained after nitrooxidation showed the presence of a carbonyl function and the absence of a peroxynitrate function and the product was identified as a mixture of nitroketonized amides including N-( l0-nitro-9-octadecanonyl)-N'-(9- octadecenoyl)-l ,3-diaminopropane, N-(10-nitro-9- octadecanonyl) -N-(9-octadecenoyl)-1,3- diaminopropane, N-(9-nitro-l0-octadecanonyl)-N-(9- octadecenoyl)-l ,3-diaminopropane, N-(9-nitro-10- octadecanonyl)-N-(9-octadecenoyl)-1,3- diaminopropane, N-(9-octadecenyl)-N l0-nitro-9- octadecanonoyl)-1,3-diaminopropane, N-( 9- octadecenyl)-N-( l 0-nitro-9-octadecanonoyl)-l ,3- diaminopropane, N-(9-octadecenyl)-N'-(9-nitro-10- octadecanonoyl)-l ,3-diaminopropane and N-(9- octadecenyl)-N-( 9-nitrol 0-octadecanonoyl)-l ,3- diaminopropane.

EXAMPLE 11 Example I was repeated employing 14.7 grams toluene as the inert solvent and simultaneously contacting the solution with oxygen introduced at the rate of 60.8 milliliters per minute and dinitrogen tetroxide at the rate of 0.0086 moles per minute for 2.9 hours. A product yield of 12.0 grams was obtained and identified as a mixture of nitroketonized amides as in Example 1.

EXAMPLE 111 To a solution of 25.5 grams (0.05 mole) of N-(9- octadecenyl)-N-octanoyl-1,3-diaminopropane in 300 milliliters of n-pentane as inert solvent, there was added simultaneously oxygen at the rate of 60.8 milliliters per minute and dinitrogen tetroxide at the rate of 0.018 moles per hour for 2.75 hours at 0C. After 2.75 hours 3.1 m1. of liquid dinitrogen tetroxide (0.05 mole) had been transferred to the reaction flask and the solution was purged with oxygen for about one hour. The solution was mixed with water forming an emulsion and pentane was stripped under vacuum and replaced with ether. The aqueous layer was separated and the organic layer was washed three times with 100 ml. portions of water. The organic layer was dried over anhydrous sodium sulfate, the latter removed by filtration and the solvent stripped from the product under vacuum. A yield of 12.9 grams of a product identified as a mixture of N-( l0-nitro-9-octadecanonyl)-N-octanoyl-1,3- diaminopropane and N-(9-nitro-l0-octadecanonyl)- N'-octanoyl-1,3-diaminopropane was recovered.

EXAMPLE IV To a solution of 28.3 grams (0.05 mole) of N-(C alkyl-N-(9-octadecenoyl)-1,3-diaminopropane in 300 milliliters of carbon tetrachloride as inert solvent, there was added simultaneously oxygen at the rate of 60.8 ml. per minute and dinitrogen tetroxide at the rate of 0.015 moles per hour for 3.2 hours at 0C. After 3.2 hours 3.1 ml. of liquid dinitrogen tetroxide (0.05 mole) had been transferred to the reaction flask and the solution was purged with oxygen for about one hour. The reaction mixture was washed three times with 100 ml. portions of water. The organic layer was dried over anhydrous sodium sulfate and the solvent was stripped from the product under vacuum. A yield of 18.8 grams of a product identified as a mixture of N-(C alkyl- N'-( 10-nitro-9-octadecanonoyl )-1 ,3-diaminopropane and N-(C alkyl-N'-(9-nitro-10-octadecanonoyl)- 1,3-diaminopropane was recovered.

EXAMPLE V The base fuel employed in the following examples was a premium grade gasoline having a research octane number of about 101.5 containing 3.0 cc. of tetraethyllead per gallon. This gasoline consisted of about 25 percent aromatic hydrocarbons, 14.5 percent olefin hydrocarbons, 60.5 percent paraffinic hydrocarbons and boiled in the range of about F. to 380F.

A gasoline blend was prepared consisting of the above base fuel containing 5 PTB (pound per 1000 barrels of gasoline) of an acid amide mixture of N-(9- octadecenyl)-N'-(9-octadecenoyl)-1 ,3- diaminopropane and N-(9-octadecenyl)-N-(9- octadecenoyl)-l ,3-diaminopropane. Another gasoline blend was prepared consisting of the above base fuel containing 5 PTB of the nitroketonized acid amide reaction product of Example I. The base fuel and each of the additive-containing gasoline blends were tested and compared for their carburetor detergency' properties in line in preventing the build-up of deposits in the car'bu retor. The gasoline blend containing the nitroketonized acid amide additive was 63 percent more effective than the base gasoline in preventing the build-up of deposits in the carburetor.

EXAMPLE VI To a solution of 14.7 grams (0.025 mole) of a mixture of N-(9-octadecenyl)-N'-(9-octadecenoyl)-l,3- diaminopropane and N-(9-octadecenyl)-N-(9- octadecenoyl)-l ,3-diaminopropane in 200 ml. of nhexane as inert solvent, there was added simultaneously oxygen at a rate of 60.8 milliliters per minute and dinitrogen tetroxide at the rate of 0.019 mole per hour for 2.7 hours at C. After 2.7 hours, 3.0 milliliters of liquid dinitrogen tetroxide (0.05 mole) had been transferred to the reaction flask and the solution was purged with oxygen for one-half hour. Dimethylformamide (15 ml.) was added to the reaction solution dropwise over a period of 8 minutes at 2 to 5C. The solution was mixed with 100 milliliters of 5 percent aqueous sodium bicarbonate. Hexane was removed from the resulting mixture and replaced with 400 milliliters of benzene. The aqueous phase was separated and the benzene layer was washed three times with 200 milliliter portions of water. The benzene solution was dried over anhydrous sodium sulfate, the latter removed by filtration and the solvent stripped from the product under vacuum. A yield of 7.3 grams of a product composed of a mixture of N-( l0-nitro-9- octadecanonyl)-N-( -nitro-9 octadecanonoyl)-1,3- diaminopropane, N-( 10-nitro-9-octadecanonyl)-N- (10-nitro-9-octadecanonoyl)-l ,3-diaminopropane, N- (l0-nitro-9-octadecanonyl )-N '-(9-nitrol 0- octadecanonoyl)-l ,3-diaminopropane, N-( l0-nitro-9- octadecanonyl )-N-( 9-nitrol O-octadecanonoyl) l ,3- diaminopropane, N-(9-nitro-10-octadecanonyl)-N (10-nitro-9-octadecanonoyl)-l ,3-diaminopropane, N- (9-nitro-10-octadecanonyl)-N-( l0-nitro-9- octadecanonoyl)-l,3-diaminopropane, N-(9-nitro-l0- octadecanonyl )-N -(9-nitrol 0-octadecanonoyl)-l ,3- diaminopropane and N-(9-nitro-lO-octadecanonyl)-N- (9-nitrol 0-octadecanonoyl)-l ,3-diaminopropane was obtained.

The base fuel employed in this example was a premium grade gasoline having a research octane number of about 102.0 containing 2.86'cc of tetraethyllead per gallon. This gasoline consisted of about 34 percent aromatic hydrocarbons, 9 percent olefinic hydrocarbons, 57 percent paraffinic hydrocarbons and boiled in the range of about 90F. to 380F. A gasoline blend was prepared consisting-of the base fuel containing 32 PTB of nitroketonized reaction product recited in Example VI. The base fuel and gasoline blend above were tested for the carburetor anti-icing properties. The stalling time of base fuel at 0.5 inches of mercury was 47 seconds and at 0.9 inches of mercury was 54 seconds. The gasoline blend containing 32 pounds per thousand barrels of the nitroketonized reaction product at 0.5 inches of mercury was 260 seconds and at 0.9 inches of mercury was 274 seconds. f

8 Another gasoline blend was prepared consisting of the above base fuel and containing 32 PTB of the nitroketonized acid amide of Example II. The stalling time of this gasoline blend at 0.5 inches of mercury was 231 seconds and at 0.9 inches of mercury was 264 seconds.

The anti-rusting properties of the base fuel alone and base fuels containing 32 pounds per thousand barrels of the nitroketonized reaction products of Examples II and VI respectively were determined employing the 10 test procedure heretofore described. An examination of the cold-rolled steel strip contacted with the fuel layer in the base fuel revealed that about 95 percent of the surface area had rusted. In comparison, the base fuels containing respectively the nitroketonized products of Examples II and VI showed zero percent rusting of the surface area contacted with the fuel layer.

EXAMPLE VII The nitroketonized product of Example I was evaluated to determine its affect, if any, on a motor fuels re- 0 search octane at various concentrations with the results tabulated below.

Additive In Gasoline Containing 3cc TEL/gallon Research Octane Number None (base gasoline) N troketon zed amide 64 PTB Nitroketon zed amide 128 PTB Nitroketomzed amide 256 PTB From the tabulation it will be seen that even at high where R is an alkenyl group having from 4 to carbon atoms, where R and R alternately represent hydrogen and an alkenoyl group having from 4 to 40 carbon atoms with dinitrogen tetroxide and oxygen at a temperature of from about 35 to C.,

wherein the mole ratio of said acid amide to dinitrogen tetroxide to oxygen is from 112:2 to 1:4:60.

2. A method according to claim 1 wherein said contacting is conducted at a temperature of from 10 to 30C.

3. A method according to claim 1 wherein said acid amide comprises a mixture of N-(9-octadecenyl)-N- (9-octadecenoyl)-l,3-diaminopropane and N-(9- octadecenyl)-N-( 9-octadecenoyl)-l ,3- diaminopropane.

4. A method according to claim 1 wherein R, R Or R has from 8 to 22 carbon atoms.

5. A method according to claim 1 wherein said nitroketonized amide is N-( l0-nitro-9-octadecanonoyl)- N-( l0-nitro-9-octadecanonoyl)-1,3-diaminopropane.

6. A method according to claim 1 wherein said nitroketonized amide is N-(l0-nitro-9-octadecanonyl)- N-( l0-nitro-9-octadecanonoyl )-l ,3-diaminopropane.

7. A method according to claim 1 wherein said nitroketonized amide is N-(9-nitro-l0-octadecanony N'-( 10-nitro-9-octadecanonoyl l ,3-diaminopropane.

8. A method according to claim 1 wherein said nitroketonized amide is N-(9-nitro-IO-octadeCanOnyD- N-(9-nitrol 0-octadecanonoyl )-l ,3-diaminopropane.

Claims

1. A METHOD OF PREPARING A NITROKETONIZED AMIDE WHICH CONSISTS ESSENTIALLY OF CONTACTING AN ACID AMIDE OF THE FORMULA:

2. A method according to claim 1 wherein said contacting is conducted at a temperature of from -10* to 30*C.

3. A method according to claim 1 wherein said acid amide comprises a mixture of N-(9-octadecenyl)-N''-(9-octadecenoyl)-1,3-diaminopropane and N-(9-octadecenyl)-N-(9-octadecenoyl)-1,3-diaminopropane.

4. A method according to claim 1 wherein R1, R2 or R3 has from 8 to 22 carbon atoms.

5. A method according to claim 1 wherein said nitroketonized amide is N-(10-nitro-9-octadecanonoyl)-N''-(10-nitro-9-octadecanonoyl)-1,3 -diaminopropane.

6. A method according to claim 1 wherein said nitroketonized amide is N-(10-nitro-9-octadecanonyl)-N-(10-nitro-9-octadecanonoyl)-1,3 -diaminopropane.

7. A method according to claim 1 wherein said nitroketonized amide is N-(9-nitro-10-octadecanonyl)-N''-(10-nitro-9-octadecanonoyl)-1,3 -diaminopropane.