US3554712A - Gasoline containing n-sulfinyl amine - Google Patents

Abstract

GASOLINE CONTAINING AS AN ANTIKNOCK AGENT AN N-SULFINYL AMINE COMPOUND, IS DESCRIBED.

Description

United States Patent Ofice GASOLINE CONTAINING N-SULFINYL AMINE George C. Licke, Oxford, Mich., assignor to Ethyl Corporation, New York, N.Y., a corporation of Virginia N Drawing. Filed Dec. 20, 1968, Ser. No. 785,804 Int. Cl. C101 1/22 U.S. Cl. 44-74 10 Claims ABSTRACT OF THE DISCLOSURE Gasoline, containing as an antiknock agent an N-sulfinyl amine compound, is described.

BACKGROUND OF THE INVENTION This invention is directed to the use of N-sulfinyl amines as gasoline antiknock agents.

The octane number of a gasoline is improved by addition of an antiknock agent. The most commonly used antiknock agents are organolead compounds such as tetraethyllead. Sulfur containing compounds in gasoline, on the other hand, are generally detrimental to octane number.

The present invention provides a novel, sulfur containing non-metallic organic compound as an antiknock agent.

SUMMARY OF THE INVENTION Gasoline containing an antiknock quantity of an N- sulfinyl amine.

DESCRIPTION OF PREFERRED EMBODIMENTS An embodiment of this invention is gasoline containing an antiknock quantity of a compound having the formula R- [N SOH- (I) wherein x is an integer from 1 to 4 inclusive, preferably 1 to 2 inclusive, and R is selected from (a) C -C alkyl groups (b) C C aryl groups (c) C -C alkenyl groups, and

(d) alkylene amino groups having the formula where R and R are independently selected from hydrocarbon alkyl groups having from 2 to about 4 carbon atoms, and y is 0 to 6. Gasoline which is substantially free of organolead compounds is preferred.

Another preferred gasoline composition contains N- sulfinyl aryl amines having 6 to about 30 carbon atoms. The amount of N-sulfinyl amine compound present in the gasoline ranges from 0.1 to about 10 gram-mols per gallon. The N-sulfinyl mononuclear aryl amines having 6 to 18 carbon atoms are more preferred. N-sulfinyl aniline and N-sulfinyl substituted anilines such'as N-sulfinyl toluidine are especially preferred.

The N-sulfinyl amines used in the invention are defined by Formula I above. Methods of preparing these compounds are available in the art. A representative method of preparing these compounds is direct treatment of the parent primary amine with thionyl chloride in a suitable 3,554,712 Patented Jan. 12, 1971 solvent. The reaction is illustrated by the following equation:

As the equation illustrates, an N-sulfinyl amine is a derivative of a primary amine in which the two amine hydrogens are replaced by the radical. In general then, the N-sulfinyl derivative of any suitable primary amine can be used as a gasoline anti-knock in the practice of this invention, provided that it has sufiicient solubility in gasoline to effect octane number improvement.

Preferred N-sulfinyl amines are those in which the R in the Formula I above is selected from the Groups (a)- (d) listed above. N-sulfinyl amines in which R is a C -C alkyl group include linear, cyclic, and branched alkyl groups with one or more sulfinyl moieties. Representative examples of N-sulfinyl amines are:

N-sulfinyl-n-pentylamine, N-sulfinyl-n-octadecylamine, N-sulfinyl-2-ethyl-n-hexylamine, N-sulfinyl-2,4,4,6,G-pentamethyl-n-heptylamine, N-sulfinyl cyclohexylamine,

N-sulfinyl cyclopentylamine,

N-sulfinyl cyclooctylamine,

N-sulfinyl laurylamine,

and the like.

Representative examples of N-sulfinyl alkyl amines having more than one sulfinyl group are:

N,N-disulfinyl-1,5-pentanediamine,

N,N-disulfinyl-l,lO-decanediamine,

N,N',N",N-tetrasulfinyl-(2,3 methylamine) 1,4 butanediamine,

N,N',N"-trisulfinyl-l,6,l2-dodecanetriamine N,N-disulfinyll l 8-octadecanediamine,

and the like.

N-sulfinyl amines wherein R in Formula I is a C -C aryl group can have one or more sulfinyl groups; and R can be an unsubstituted aryl group, substituted aryl group, alkaryl and aralkyl group, mononuclear as well as polynuclear aryl group. Representative examples of these N-sulfinyl aryl amines are:

N-sulfinyl-p-cyclohexylaniline, N-sulfinyl-2,-dichloroaniline, N-sulfinyl-[i-naphthylamine, N-sulfinyl-4-diphenylamine, N-sulfinyl-4-dodecylaniline, N-sulfinyl-2,4-didodecylaniline, N-sulfinyl-2,4'dimethylamine,

N-sulfinyl benzylamine, N-sulfinyl-a-anthracenylamine, N-sulfinyl-Z-isopropylaniline, N-sulfinyl-4-octadecylaniline, N-sulfinyl-2,4,6-triethylaniline, N-sulfinyl-N'-phenyl-phenylenediamine, N,N'-disulfinyl-4,4'-diphenyldiamine, N,N,N"-trisulfinyl-l,3,5-benzenetriamine, N,N',N",N"'-tetrasulfinyl-1,2,4,6-benzene tetramine, N,N'-disulfinyl-benzidine, N,N'-disulfinyl-3,3'-dichlorobenzidine, and the like.

More preferred N-siilfinyl aryl amines are those derived from lower aryl mononuclear mono and diamines having from 6 to about 18 carbon atoms. Representative examples of these N-sulfinyl aryl amines are:

N-sulfinyl amines where R in Formula I is an alkenyl group include monoas well as poly-unsaturated alkenyl compounds. Representative examples of these N-sulfinyl alkenyl amines are N-sulfinyl allylamine. N-sulfinyl oleylamine, N-sulfinyl linoleylainine, N-sulfinyl-4-pentenvl amine, N-sulfinyl-Z-heptenyl amine, N.N'-disulfinyl-6- dodecenyl-l,l2-diamine, and the like.

N-sulfinyl amines where R is the group represented by [RFLU R wherein R R and y are as defined above. are derived from C C alkylene diamines and polyamines. Representative examples of these types of N-sulfinyl amines are:

Mixtures of N-sulfinyl amine compounds described above can also be used in gasoline compositions of the present invention.

Any gasoline suitable for use in internal combustion engines may be used in the practice of this invention. By

gasoline is meant a hydrocarbon or blend of hydrocarbons boiling in the range from about 25 C. to about 250 C. which occur naturally in petroleum as Well as suitable hydrocarbons manufactured from petroleum. for example. by thermal or catalytic cracking, polymerizing, reforming, and the like. Typical gasolines are listed in Table I.

TABLE I.IIYD ROCARBON COMPOSITION OF BASE GASOLINES Base gasoline lI \'(llOCt1ll)0l1 type A '3 C D E T Aromatics. percent L10. 27. 0 34. 5 19.0 .0 Oltlnis. percent" 4.5 11. 0 K. 0 1R. 5 .5 Siittirntt-s. pun-t t s5. 0 62. i) 07 5 l3). 5 '3 J, in the handling of gasolines in refineries, tanks. pipelines, tc the gasoline may pick up traces of organolead com- 10unt1s. The term "substantially free of organolead comounds indicates gasoline that has picked up this minor generally less than about 0.1 gram of lead per gallon) .mount of organolead compounds.

"he amount of N-sulfinyl amine which is added to the me gasoline to prepare gasoline compositions of the resent invention may be aried. The term "antiknock auantity means an amount of N-sulfinyl amine sutficient 0 increase the octane number or' the base gasoline. Gen- :raily from about 0.1 to about 10 gram-mols of the l uifinyl amine can be added per gallon of base gasoline. l gram-mol is the molecular weight of the amine expressed in grams. For example. if the N-sulfinyl amine .dditive has a molecular weight of 100 then gasoline comiositions or the present invention could contain as little is l gram or as much as 1000 grams of the amine per gallon of gasoline.

The gasoline compositions of the present invention do tot require any special method of preparation. The addiive can simply be added directly to the gasoline and .tlended using any conventional blending means. In addition to the novel N-sulfinyl amine antiknock additive. the present gasoline composition may contain other additives arovided that they do not adversely affect the function it the N-sulfinyl amine; such gasoline additives include ion-organolead antiknock agents such as (cyclopentadi- :nyllmanganese tricarbonyl. antioxidants such as the hindered phenols. dyes. anti-icing additives. carburetor detergents such as fatty acid amino-amides. corrosion innibitors. metal deactivators. and the like. If desired, antitnock fluids or concentrates may be prepared containing he N-sulfinyl amines and any combination of other additives and/or diluents.

he feature of the present invention is that the N-sullnyl amines described above are antiknock agents in gasliines. In other words. gasolines containing N-sulfinyl tmines have improved octane ratings, This was demonstrated by blending a series of fuels containing from about 0.5% to about 5.0% by volume of certain N-sulfinyl mines. The Research Octane Number (RON) of the base uel alone and the base fuel containing the sulfinyl addiwe were determined using the method of ASTM D908. The antiknock effect was expressed as the difference ARON) between these two Research Octane Numbers. "he data obtained for a series of fuel compositions demtnstrating this antiknock erfect is contained in Table II "elow.

ABLE II. NSULFINYLAMINES IN BASE GASOLINE A.

.mount of idditive 'olume. percent .xainple additive urinals/gal.) RON l ARON '17. 65 E8. 05 l. 40 )8. l. 55 )8. 00 1.

. 97.90 0. 5 )8. 15 I. 25 ido l. 0 )8. 0. .lo 5.0 100.40 3.50 t .q-Slllfillyltlllllllm 5. 0 100. 35 J. l5

kvcrage of two determinations.

The Research Octane Number data of Examples l9 amply illustrate the beneficial effect of N-sulfinyl amines n gasoline.

The following examples further illustrate compositions 0 of the present invention. These compositions are prepared TABLE III Base gasoline Example Additive Amount of N-sulfinyl-p-tert-butylaniline. N ,N-disulfinyl-1,3-propane diamlne N -sultlnyl-4-pentenylamiue N-sulflnylcyelohexylamiue The gasoline compositions of the present invention have been fully described above. Data is presented to show the antiknock efiectiveness of the N-sulfinyl amines in these gasoline compositions.

I claim:

1. Gasoline containing an antiknock quantity of a compound having the formula R- [N=SO] wherein x is an integer from 1 to 4 inclusive and R is selected from the group consisting of (a) C C alkyl groups (b) C -C aryl groups (c) C -C alkenyl groups, and

(d) alkylene amino groups having the formula 4. A gasoline of claim 2 wherein R is a C -C aryl group.

5. A gasoline of claim 3 wherein x is an integer from 1 to 2 inclusive.

6. A gasoline of claim 4 wherein R is a C -C mononuclear aryl group.

7. The gasoline of claim 6 wherein said compound is N-sulfinyl-p-toluidine.

8. A gasoline of claim 6 wherein said compound is N-sulfinyl aniline.

9. A gasoline of claim 7 wherein the concentration of said compound is from about 0.5 to about 5% by volume.

10. A gasoline of claim 8 wherein the concentration of said compound is from about 0.5 to about 5% by volume.

U.S. C1. X.R.