US3158450A

US3158450A - Triazinyl derivatives as gasoline additives

Info

Publication number: US3158450A
Application number: US157856A
Authority: US
Inventors: Alelio Gaetano F D
Original assignee: Dal Mon Research Co
Current assignee: Dal Mon Research Co
Priority date: 1961-12-07
Filing date: 1961-12-07
Publication date: 1964-11-24
Anticipated expiration: 1981-11-24

Description

United States Patent 3,158,450 TRIAZWYL DERIVATTVES AS GASOLINE ABDKTIVES Gaetano F. DAlelio, South Bend, Ind, assignor, by direct and mesne assignments, to Dal Mon Research (30., Cleveland, Ohio, a corporation of Delaware No Drawing. Filed Dec. 7, 1961, Ser. No. 157,856 '29 Claims. (Cl. 44-63) This invention relates to improvements in gasoline-type motor fuels.

To increase the anti-knock value of gasoline-type motor fuel, such fuels are modified by the addition of a tetraalkyl lead, such as tetramethyl lead or tetraethyl lead with a lesser amount of halohydrocarbon, such as an alkyl or alkylene halide, as for example, ethylene dichloride, ethylene dibromide, carbon tetrachloride, and the like. The mixture of a tetraalkyl lead and a haloalkane is known as ethyl fluid and is used extensively in automotive and aviation gasolines in amounts of 1 cubic centimeter to 4 or 5 cubic centimeters per gallon of gasoline.

In the modern high compression engine, even though the use of ethyl fluid is beneficial, its use tends to cause surface or pro-ignition, which results in rnisfiring and disrupts the regular rhythm of engine operation. This surface ignition in gasoline containing lead derivatives is due to the deposition of various lead compounds within the combustion chamber of the engine, which thereafter produces hot spots or glow points in the combustion chamber, causing pre-ignition and pro-combustion.

Another adverse eifect which results from the use of leaded gasoline is misfiring of the engine due to sparkplug fouling. Though the use of halohydrocarbon scavengers has only partially remedied the problems resulting from the deposition of lead compounds in the combustion chamber, it has been less effective in the prevention of spark-plug fouling, which particularly in aircraft gasoline combustion engines, is a serious problem.

It has now been found that the above disadvantages accompanying the use of leaded gasoline can be substantially minimized and even eliminated by the addition of a small amount of certain 1,3,5-triazine phosphonic acid derivatives to leaded gasoline, thereby reducing pre-ignition and spark-plug fouling to a significant degree. The additives of this invention are derivatives of 1,3,5-triazines,

represented herein as C N to which is attached, through the carbon atoms of the triazine ring, at least one phosphonium moiety,

Since the triazinyl radical is trivalent, these derivatives can contain no more than three such phosphonium groups,

3,158,450 Patented Nov. 24, 1964 The only requirement for the compounds used in the practice of this invention is that they contain at least one such phosphonium group, and thus, though the other valencies of the triazine ring may be occupied by any monovalent radical, certain advantages accrue, as hereinafter shown, when more than one phosphonium group is present, or when the other monovalent radicals are especially selected to perform a special or selected function. These triazine derivatives may also be expressed by the formula ice in which n represents a numerical value of 1 to 3, A represents a radical selected from the class of wherein B is selected from the class of oxygen and sulfur, R represents a radical selected from the class consisting of hydrogen, a hydrocarbon radical containing from one to twenty carbon atoms, the hydroxy and halogenated derivatives of said hydrocarbon radicals, M represents a metal selected from the class of alkaline and alkaline earth metals, K represents a radical selected from the class of BR, BM, and NR (where the oxygen derivatives are to be specified K is substituted for K), and Y represents a monovalent radical. For ordinary usage the nature of the monovalent radical Y is not critical since the efiect of the phosphonium radical on the lead is not affected. For example, Y can be H, R, -BH, Br, -NR, --NRNR halogen, and the hydroxy-, halogeno-, acetoxy, alkoxy, carbamido and sulfamido derivatives of the R group such as However, when it is desirable to impart special properties to the triazinyl phosphonium derivatives used in the practice of this invention, such as increased solubility in petroleum products, then R represents a hydrocarbon radical possessing from 5 to 20 carbon atoms. When it is desired to impart further special properties to these compounds, such as antioxidant properties, and to retain solubility in hydrocarbons, or to have these compounds act as stable halogen carriers, while considering also economic factors and availability of raw materials, then, preferably Y is R'-, R'B or R N wherein R represents radicals contining 5 to 20 carbon atoms selected from the class of R, halogenated derivatives of R and hydroxy aryl radicals such as l a a)i: s)2 s is used, whereas if a high carbon content is desired, the higher alcohol esters are satisfactory, thus ll a a) i: P 18 31): 3 Furthermore, if a detergent property is desired, the tri azinyl phosphonium ester may be saponified to produce the monoor di-salt, thus 2 a)[ 19-0 CHE-37 O a a) [ii -0 01211 ONa o lLsONa If a non-ionic type detergent is desired, the phosphonic acid can be reacted with an alkylene oxide to obtain such a product, thus Y a e) wherein n has a numerical value of 3 to 15.

The phosphonium moiety can also act as a carrier of halogen atoms thus t (OCHgCH4Cl)g and 1 (OCH CH C1) It can also be a carrier of an antioxidant structure, thus 0 t -l' '-NHC H4OH OCeH4 It can also serve in a joint function as a halogen carrier and antioxidant, such as in the moiety The compounds used in the practice of this invention are prepared readily by the reaction of a halo-s-triazine with a phosphite ester as follows:

It is obvious from the foregoing that these additive compounds, because of the various reactions that can be effected by the phosphites, P(OR) with either a mono-, di-, or tri-halo triazine, can be synthesized to contain more than the phosphorus atoms as phosphates or phosphites, and therefore can perform more functions when used as an additive. Furthermore, since the phosphonium structure is attached to a triaz-ine ring which contains nitrogen in a relatively inert form, the combustion of these compounds produces oxides of nitrogen which also assist in removal of combustion cylinder deposits.

The synthesis of typical compounds used in the practice of this invention is illustrated in the following examples. Unless specified otherwise, parts and percentages recited herein are parts and percentages by weight.

Example 1 One hundred thirteen (113) parts of cyanuric chloride is added gradually to 575 parts of triethyl phosphite over a period of 1 hour. During the addition considerable heat is generated and some ethyl chloride is liberated. The resultant mixture is maintained at 9046? C. for 1 hour and then allowed to cool to room temperature. The cooled mass is extracted with low boiling petroleum ether to remove excess triethyl phosphite and then recrystallized from ethyl ether. The crude yield is about 99 per cent, and the melting point of the recrystallized product is 94-95 C. Analyses show 38.36% carbon and 6.12% hydrogen, which correspond closely with the theoretical values of 36.84% carbon and 6.11% hydrogen for the compound having the formula When other phosphites of the formula P(OR) and P(SR) are used instead of the triethyl phosphite with R representing butyl, amyl, cyclohexyl, phenyl, chlorphenyl and acetoxyphenyl, the corresponding triazine phosphonium and thiophos'phonium derivatives are obtained.

Example II Example I is repeated using an equivalent amount of trimethyl phosphite instead of triethyl phosphite and there is obtained.

0' Ca s[( OH3)2]3 of melting point 124.5 C., which on analysis shows C, 26.89% and H, 4.68%, which is in good agreement with the calculated values for carbon and hydrogen.

Example Ill Example I is repeated, using molar equivalents of trin-propyl phosphite instead of triethyl phosphite, and there is obtained.

7 0 caNs -i i afldz as an oil which slowly crystallizes on standing at 0 C. Example IV Example I is repeated using molar equivalents of tri- (beta-chloroethyl)phosphite instead of triethyl phosphite and there is obtained melting point 53-54 C., which on analysis shows 25.59% C' and 3.38% H, which compares with the theoretical values of 25.86% C and 3.45% H respectively.

Example V Example I is repeated using molar equivalents of triallyl phosphite instead of triethyl phosphite, and there is obtained which on analysis and molecular weight determination give values in close agreement with the theoretical values for this compound. When the trimethylallyl phosphite is used in equivalent amount instead of the triallyl phosphite, there is obtained s ai: 2 2)21a Example VI One hundred fifty (150) parts of are added to 200 parts of carbon tetrabromide and 80 parts of bromine added to the mixture at 20-50 C. and there is obtained in solution in ethylene dibromide, the compound.

0 ii a si:P(OCHzCHBrCH Br) 3 This solution can be used in lead gasoline as such, or the halogenated phosphonium triazine derivative isolated by removal of the carbon tetrabromide under reduced pressure. When the methallyl derivative is used instead of the allyl derivative, there is obtained 1'? CH3 1 caN amoornhnrongBm 3 Example VIZ In a suitable reactor equipped with stirrer and reflux condenser a mixture of 145.5 parts of 2,4-diamino-6- is obtained, which on analysis gives values of 35.16% carbon, 5.89% hydrogen, 15.35% nitrogen, and 17.21% phosphorus. These values are in close agreement with the theoretical values.

When this diester is allowed to stand at 'room temperature with aniline, the corresponding is obtained.

Example VIII The procedure of Example I is repeated, using trioctylphosphite in molar quantities equivalent to triethylphosphite, and there is isolated the compound Similarly, the triesters of decyl, dodecyl, tetradecyl, and octadecyl alcohols are prepared.

Example IX One hundred thirty-seven parts of 2-chloro-4,6-dihydroxy-s-triazine prepared from cyanuric chloride by the method given in J. prakt. Chem, (2), 75, 103 (1907) are reacted with 104 parts of trimethyl phosphite according 6 to the procedure of Example I. A quantitative yield of 0 (HO): as)2 is obtained. When an equivalent weight 2,4-dichloro-6- hydroxy-s-triazine is used instead of the 2-chloro-4,6-dihydroxy compound, the corresponding derivative HOC N [PO'(OCH is obtained in quantitative yield.

When

is treated with aniline, methyl amine and dietnyi amine respectively, according to the procedure of Example VII, the corresponding amides are obtained respectively,

Example X Two hundred thirty-six parts of HOC H NH(C N )CI prepared according to the procedure of US. Patent 2,393- 755, in 250 parts of benzene are refluxed ten hours with parts of tri-ni-propyl phosphite. Then the benzene is removed under a reduced pressure, using a Water aspirator, to give a quantitative yield of crude but relatively pure l HOCaH4NHCa si: 3 02 a When an equivalent amount of (HOC H NH) C N CI (see US. Patent 2,393,755) is used instead of the dichloro-triazine of this example, there is obtained 0 i H (HOC HANHM a a- B M Treatment of these phosphonic esters with the amines of Example D( by the procedure of Example VII produce the corresponding phosphonamides, whereas when diethyl amine or decyl amine is used, there is obtained respec tively HOCgHaNH-CzNg- Example XI Z-amino-4,6-dichloro-s-triazine prepared according to the method of Berichte, 32, 6 91 (1889), is'converted to 2-amino-4-hydroxy-6-chloro-s-triazine by the hydrolysis procedure of J. prakt. Chem, .(2), 75, 103 (1907). Thereafter, 136 parts of 2-amino-4-hydroxy-6-chloro-striazine are reacted with 250 parts of tri-n-butyl phosphite according to the procedure of Example I, and there is obtained (HO) z 3 3- edit)? Example XII One hundred thirty-eight parts of 2-amino-4,6-dichloros-triazine are mixed with 250 parts of tri-secondary butyl phosphite and allowed to react in a suitable container at room temperature for twenty-four hours, and at 60 C. for 8 hours; there is obtained on recrystallization of the reaction product from acetone-water a substantial yield of it (01) (N112) a a (0 41 192 Example XIII Two hundred and fifteen parts of 2-phenyl-4,6-dichloros-triazine prepared by the procedure of US. Patent 1,911, 689 is reacted by the procedure of Example II with 210 parts of trimethyl phosphite, and there is obtained Treatment of this product with ammonia, and aniline according to the procedure of Example VII results in Example XIV One hundred and nine parts of are heated at 100 C. with 210 parts of phenol containing 1 part of magnesium oxide for 14 hours or until methanol is no longer released from the reaction. From the reaction product there is obtained When this procedure is repeated with p-chloro phenol, there is obtained 0 ll CBHB CINQ[ O 011E401] 065114 1 2 Example XV 2,4-di-o-dichlorophenyl-6-chloro-s-triazine is prepared by the method of Chem. Ztg. 36, 378 (1912), and when this product is used in the procedures of Examples VII, IX, and XIV there is obtained respectively Example XVI ll (C4130) (NHQO C GEES) C3N -P (0 051111):

Example XVII Thirty parts of 10 parts of 37.1% CH aqueous solution and 0.1 part of NaOH are mixed and allowed to stand 48 hours at room temperature, or until substantially all of the formaldehyde has disappeared and there is obtained a dispersion in Water of the compound.

The addition of 4.5 parts of dimethyl amine or 7 parts of diethyl amine to this compound at room temperature produces, respectively,

O H 1 (CH )nNCHzNHCsNzi:P 2 5): 2

O (Q2H5) 2NG zNH s ai: {I} (O gHsh]: Example XVIII Two hundred ten parts of II (N 2): a a) P M 165 parts of 37% formaldehyde aqueous solution, and 3 parts of KOH are allowed to stand at room temperature with constant agitation for 48 hours, or until substantially all of the formaldehyde has disappeared and there is obtained a dispersion of the compound 0 H 11o OH NHhC Ng-(P 0 CH3): which is dried in a vacuum at room temperature.

Example XIX Two hundred parts of '2,l-di-ethylamirip-dchloro-s-trh azine prepared by the method of JACS 73, 2982 (1951) is reacted with parts of triethyl phosphite as in the procedure of Example II, and pound r u I B M a a- 2 5):

When 203 parts of P(SC H are substituted for the P(OC H of this examplethe corresponding compound,

is obtained, which when reacted with aniline according to the procedure of Example I, yields there is obtained the com- 9 Example XX Z-dimethylaminol,6-dichloro-s-triazine is prepared according to the procedure of JACS 73, 2982 (1951) and converted to the 4-thiocarbamyl methyl sulfide,

by the method given in US. Patent 2,295,562. This is reacted with triethyl phosphite by the procedure of Example IX to give ll (CHQNH) (HQNO C CH S) C N -P (O C l-I) 2 Example XXI 2-chloro-4,6-dimethoxy-s-triazine is prepared according to the procedure of IACS 73, 2989 (1951) and reacted with one molar equivalent of triallyl phosphite according to the procedure of Example I yields Example XXII 2,4-dichlcro-6-methoxy-s-triazine is prepared according to the procedure of IACS 73, 2989 (1951) and reacted with two molar equivalents of trimethyl phosphite by the procedure of Example I to give O (CHaO) 2 2[ i) 02 9212 Substitution of 2,4-dichloro-6-phenoxy-s-triazine for the corresponding methoxy derivative in this example produces Example XXIII Sulfanilamide is reacted with cyanuric chloride 2,4-dichloro-6-(4-sulfamoylanilino)-s-triazine according to the method of J. Org. Chem., 24, 643 (1959), and when this compound is reacted with two molar equivalents of triethyl phosphite according to the procedure of Example 11, there is obtained the compound When 2-chloro-4,6-di-(l-sulfamoylanilino)-s-triazine is used instead of the above dichloro-compound with at least one molar equivalent of triethyl phosphite, there is obtained instead when a-amino-4-chloro-6-(4-sulfamoylanilino)-s-triazine is used instead of the dichloro compound, then, there is obtained Example XXIV 2-ethyl-4,6-dichloro-s-triazine is prepared according to the method of US. Patent 1,911,689 .and converted by reaction with ethyl aminocaproate by the method of US. Patent 2,328,961 to When reacted with one molar equivalent of tribenzyl phosphate by the procedure of Example II produces Example XXV Equivalent quantities of 2,4-dichloro-6-(Z-hydroxyeth- 19 y1amino)-s-triazine are substituted for the dichloro-triazine of Example XV and there is obtained a good yield of HO CHQCHQNHC3N3[JI,IJ (0 0213921 When the 2-chloro-4,6-di-(2-hydroxyehylamino)-s-triazine is used with one molar equivalent of the phosphite, there is obtained.

(HO CH2CH2N )2Cs a (0 02135): Example XXVI 2,4-dichloro-6-(beta-cyanoethyl sulfide)-s-triazme 15 prepared by the method of US. Patent 2,295,561 and is treated with two molar equivalent of tri-cyclohexyl phosphite by the procedure of Example II and there is obtained 0 NC CHzCHgSCaNai l (0021 110212 When the above cyanoethyl sulfide derivative is replaced by an equivalent molar quantity of 6-carbanyl methyl sulfide prepared by the procedure of US. Patent 2,295,562, there is obtained 0 z O C 2 -C;\ 3i: (OC5H11)2]2 Example XXVI] 2,4-dichloro-6-semicarbazido-s-triazine is prepared by the method of US. Patent 2,295,565 and treated with two molar equivalent of tridecyl phosphite according to the procedure of Example II and there is obtained 0 NH C ONHNHCaNsi: (0 010E213 2]: Example XXVIII 2,4-dichioro-6-ureido-s-triazine is prepared according to the method of US. Patent 2,295,563 and reacted with tripropyl phosphite by the procedure of Example II and there is obtained 0 NH C ONHC;N i (o Caron], Example XXIX 2,4-dich1oro-6-(p-sulfamyl-phenyl carbamyl methyl sulfide) is prepared according to the method of US. 2,316,692 and reacted with tri-(p-bromobenzyl) phosphite by the procedure of Example II and then is obtained 0 H NOgSCAHgNHO C GH;SO N l: (0CH2C6H4B1)g]2 Example XXX 2,4-dichloro-6-amino-s-triazine is con tedflo 2-parahydroxyphenylcarbamyl methyl sulfide by reaction with HSCH CONHC H OH by the procedure of US. Patent 2,295,562 and when this product is reacted according to the method of Example II, With triethyl phosphite, there is obtained 0 (NH:) (Ho CflENHO C urns) C mi: i (0 0,115), Example XXXI Cyanuric chloride is converted to 2,4-dichloro-6-phenyl-s-triazine by the method of U.S. Patent 1,911,689 and by reaction with para-hydroxy benzamide (by the procedure used for HSCR CONH type compound in US.

.1 1 Example XXXII 2,4-di-octadecylamino--monochloro-s-triazine is prepared by the method given in JACS 73, 2982 (1951) and reacted with a molar equivalent of trimethyl phosphite by the procedure of Example II, and the product isolated as which when saponified by refluxing with methanolic NaOH is converted to (HaIOmNHhCaN -:i. (N3): which is water-dispersible as wetting agent, emulsifier or detergent.

If the procedure of this example is repeated using 2,4- dichloro-G-octadecylamino s triazine prepared by the method of JACS 73, 2982 (1951) and reacted with two molar equivalent of trimethyl phosphite, there is obtained 0 t sY uNH) a a)i: P M02 2 which is a more effective dispersing agent than the monocompounds. This same behavior is observed in the lower allcyl derivatives containing a total of at least carbon atoms in the aliphatic chain, thus The free acid is readily liberated from these salts by treatment with excess quantities of strong inorganic acids such as sulfuric or phosphoric acid. The free acids are useful as rust inhibitors and pickling agents, and have the formula and it (Hn sN )2( a-a)- (011):

respectively.

Other metal salts such as potassium, lithium, calcium, magnesium, silver, copper, titanium, zirconium, molybdenum, etc., such as those known metals which form both inorganic or organic salts can be prepared by the known metathesis reactions or by treatment of reaction of the oxides or hydroxides of such metals with the free s-triazine phopshonic acids.

Example XXXIII Cyanuric chloride is converted to 2,4-dimercapto-6r chloro-s-triazine by the method of l. prakt. Chem. (2), 34, 152 (1886), and when this compound is reacted with molar equivalents of trimethyl phosphite according to the procedure of Example 11, there is obtained Eatample XXXIV The procedure of Example I is repeated using molar equivalents of diphenylmethyl phosphite instead of triethyl phosphite and there is obtained o H a e)i: t t)2 ,a The utility of the s-triazinyl phosphonium compounds used in the practice of this invention may be illustrated gasoline in the following tests and has the following distillation characteristic.

(Cctane rating, 98.5.)

to which is added 4 cc. of tetraethyl lead per gallon of fuel, to which may be added ethylene dibromide (EDB) as a scavenger. The amount of EDB added used is expressed in the term, Theory EDB, which designates the amount of scavenger required to react stoichiometrically will all of the lead anti-detonant so that all of the lead atoms react with all of the halogen atoms to form PbXg, and thus one theory of halogen scavenger contains two halogen atoms for each atom of lead in the lead anti-.- detonant;

The term Theory S-T-P designates the amount of striazinyl phosphonium compound required to react stoichiometr-ically with all of the lead so that all of the lead atoms and all of the phosphorus atoms to form which may be expressed also as Pb(PO and thus only two phosphorus atoms are required for each three atoms of lead. Thus it may be seen that one mole of aNa) R): a will be 4.5 Theory S-T-P, while 0 (GaNa)[ R)2]2 will be 3 Theory S-T-P, and

, also have EDB theory value, thus using gasolines of wide boiling range and with various octane ratings. A typical gasoline used as a reference O C3N3[%(OCH2CH2G1)2]3 will be 3 Theory EDB and 4.5 Theory S-T-P.

0 omiimoomonnromnml will be 6 Theory EDB and 4.5 Theory S.T.P.

A suitable engine (such as defined in ASTM-D-908-55 and in ASTMD-357-33) suitably instrumented with electrical pressure indicators and electrical ionization gap Table I.

TABLE 1 Percent STP Additive Theories Theories Increase S-'lP EDB in misfiring time None 1 0 (d CaNaIP (0 04119213 0. 1 0. 250 O. 2 0. 5 325 0. 2 0. 1 365 0. 3 0. 6 385 ll CaNaIP (0 CuHsh]: 0. 2 0. 8 400 H C3N3[P (0 CoH4C1)2]a V O. 2 0. 6 450 l] C3N3[P(OCH2OH201)2]3 0.6 O 400 0.6 0 1 450 ll (CaNs)[P (OCH CHBICHzBIMa 1.0 0 405 0. 5 0 435 0. 7 0. 05 440 (1.? C1C H5O(C3N3)[P (O CaH4C1)z]z 0.3 0,2 415 0. 05 1. O 285 (C5H1 NH)zCsN3P-O C2115 0. 2 O. 8 385 (H) (CsNa)[P (0 CsH7)2]3 0. 5 0. 5 345 Example XXXVI The engine suitably instrumented as in the previous example to detect abnormal ignitions and pressure rises in the combustion chamber is operated with the reference gasoline containing 2.7 cubic centimeters of tetramethyl lead in the following cycles, simulating driving conditions equivalent to 1 hour at 60 miles per hour 3 hours at 30 miles per hour 6 hours of start and stop driving consisting of 2 hours idling, 2 hours accelerating to 30 miles per hour, and 2 hours decelerating to idling for a total of ten hours for the cycle, which is repeated 10 times for a total of 100 hours.

The compositions of Example XXXIV are compared in this engine under the cycle given, and all of the compositions containing S-T-P when compared with the composition containing no S-TP and 1 Theory EDB show a very substantial decrease in the percentage of pre-ignition which result in misfirings.

It also may be seen from Table I that the S-T-P compounds can be used alone or in conjunction with halohydrocarbon scavengers.

When the preceding tests are repeated using the corresponding thiophosphonium compounds, improved results are likewise noted.

The invention claimed is: p

1. A fuel consisting essentially of gasoline, a minor amount of a tetraalkyl lead anti-detonant suflicient to impart anti-knock properties to said fuel and 0.0005-3 moles, per mole of said tetraalkyl lead anti-detonant, of a s-triazinyl phosphonium compound having at least one and no more than three phosphonium radicals attached to the carbon atoms of said s-triazinyl nucleus, said phosphonium radical being selected from the class consisting of radicals, wherein B is an atom selected from the class consisting of oxygen and sulfur, R represents a radical selected from the class consisting of hydrogen, hydrocarbon radicals having no more than 20 carbon atoms therein, and derivatives of said hydrocarbon radicals having only derivative groups attached thereto selected from the class consisting of hydroxy and halo radicals, K represents a radical selected from the class consisting of -BR, BM and NR and M is a metal selected from the class consisting of alkali and alkaline earth metals.

2. A fuel consisting essentially of gasoline, a minor amount of a tetraalkyl lead anti-detonant suflicient to impart anti-knock properties to said fuel and 0.0005-3 moles, per mole of said tetraalkyl lead anti-detonant, of a s-triazinyl phosphonium compound having at least one and no more than three phosphonium radicals attached to the carbon atoms of said s-triazinyl nucleus, said phosphonium radical having the formula wherein R represents a radical selected from the class consisting of hydrogen, hydrocarbon radicals having no more than 20 carbon atoms therein, and derivatives of said hydrocarbon radicals having only derivative groups attached thereto selected from the class consisting of hydroxy and halo radicals, K represents a radical selected from the class consisting of OR, OM, NR M is a metal selected from the class consisting of alkali and alkaline earth metals.

3. A fuel of claim 2 wherein said anti-detonant is selected from, the class of tetra-ethyl and tetra-methyl lead.

4. A fuel of claim 1 wherein said anti-detonant is selected from the class of tetra-methyl and tetra-ethyl lead.

5. A fuel consisting essentially of gasoline, a minor amount of a tetraalkyl lead anti-detonant suflicient to impart antiknock properties to said fuel and 0.0005-3 moles, per mole of said tetraalkyl lead anti-detonant, of a s-triazinyl phosphonium compound having at least one and no more than three phosphonium radicals attached to the carbon atoms of said s-triazinyl nucleus, said phosphonium radical having the formula 7. The fuel of claim lin which said phosphonium compound is s a s s) 2] a 8. The fuel of claim 1 in which said phosphonium compound is C N [PO (OCH CH Cl) 3 15 9. A fuel of claim 8 in Which said anti-detonant is selected from the class of tetra-methyl and tetra-ethyl lead.

10. A fuel of claim 1 in which said phosphonium 11. A fuel of claim 10 in which said anti-detonant is selected from the class of tetra-methyl and tetra-ethyl lead.

12. A fuel of claim 1 in which said phosphonium compound is C3N3 CHZBI') 2] 3 13. A fuel of claim 12 in which said anti-detonant is selected from the class of tetra-methyl and tetra-ethyl lead.

14. The fuel of claim 1 in which said phosphonium compound is 15. A fuel of claim 14 in which said anti-detonant is selected from the class of tetra-methyl and tetra-ethyl lead.

compound is 25 16. The fuel of claim 1 in which said phosphonium G 5 )2 K 2 5)Q 17. The fuel of claim 1 in which said phosphonium compound is NH2 C3N3[PO(OC5H11)2]2 18. The fuel of claim 1 in which said phosphonium compound is s a s 17)2]a 19. The fuel of claim 1 in which said phosphoniu'm 2,685,581 Coover Aug. 3, 1954 2,751,384 Coover et al June 19, 1956 3,011,998 DAlelio Dec. 5, 1961 FOREIGN PATENTS 565,182 Canada Oct. 28, 1958 572,281 Canada May 5, 1959

Claims

1. A FUEL CONSISTING ESSENTIALLY OF GASOLINE, A MINOR AMOUNT OF A TETRAALKYL LEAD ANTI-DETONANT SUFFUCIENT TO IMPART ANTI-KNOCK PROPERTIES TO SAID FUEL AND 0.0005-3 MOLES, PER MOLE OF SAID TETRAALKYL LEAD ANTI-DETONANT, OF A S-TRIAZINYL PHOSPHONIUM COMPOUND HAVING AT LEAST ONE AND NO MORE THAN THREE PHOSPHONIUM RADICALS ATTACHED TO THE CARBON ATOMS OF SAID S-TRIAZINYL NUCLEUS, SAID PHOSPHONIUM RADICAL BEING SELECTED FROM THE CLASS CONSISTING OF