CA2226982C - Polyalkylphenoxyaminoalkanes and fuel compositions containing the same - Google Patents

Abstract

Polyalkylphenoxyaminoalkanes having formula (I), wherein R is a polyalkyl group having an average molecular weight in the range of about 600 to 5,000; R1 and R2 are independently hydrogen or lower alkyl having 1 to 6 carbon atoms; and A is amino, N-alkyl amino having about 1 to about 20 carbon atoms in the alkyl group, N,N-dialkyl amino having about 1 to about 20 carbon atoms in each alkyl group, or a polyamine moiety having about 2 to about 12 amine nitrogen atoms and about 2 to about 40 carbon atoms.
The compounds of formula (I) are useful as fuel additives for the prevention and control of engine deposits.

Description

06 Field of the Invention Og This invention relates to novel Og polyalkylphenoxyaminoalkanes. In a further aspect, this invention relates to the use of these compounds il in fuel compositions to prevent and control engine deposits.

13 Description of the Related Art It is well known that automobile engines tend to form 16 deposits on the surface of engine components, such as 1~ carburetor parts, throttle bodies, fuel injectors, intake 18 ports and intake valves, due to the oxidation and 1g polymerization of hydrocarbon fuel. These deposits, even when present in relatively minor amounts, often cause 21 noticeable driveability problems, such as stalling and poor 22 acceleration. Moreover, engine deposits can significantly 23 increase an automobile's fuel consumption and production of 24 exhaust pollutants. Therefore, the development of effective fuel detergents or "deposit control" additives to prevent or 26 control such deposits is of considerable importance and 2~ numerous such materials are known in the art.

2g For example, aliphatic hydrocarbon-substituted phenols are known to reduce engine deposits when used in fuel 31 compositions. U.S. Patent No. 3,849,085, issued 32 November 19, 1974 to Kreuz et al., discloses a motor fuel 33 composition comprising a mixture of hydrocarbons in the 34 gasoline boiling range containing about 0.01 to 0.25 volume O1 percent of a high molecular weight aliphatic 02 hydrocarbon-substituted phenol in which the aliphatic 03 hydrocarbon radical has an average molecular weight in the ~
04 range of about 500 to 3,500. This patent teaches that 05 gasoline compositions containing minor amounts of an 06 aliphatic hydrocarbon-substituted phenol not only prevent or ~
07 inhibit the formation of intake valve and port deposits in a Og gasoline engine, but also enhance the performance of the pg fuel composition in engines designed to operate at higher operating temperatures with a minimum of decomposition and 11 deposit formation in the manifold of the engine.

13 U.S. Patent No. 4,259,086, issued March 31, 1981 to 14 Machleder et al., discloses a detergent additive for fuels and lubricating oils which comprises the reaction product of 16 an aliphatic hydrocarbon-substituted phenol, epichlorohydrin 17 and a primary or secondary monoamine or polyamine. In ig addition, U.S. Patent No. 4,048,081, issued September 13, ig. 1977 to Machleder et al., discloses a detergent additive for gasoline which is the reaction product of a polyisobutene 21 phenol with epichlorohydrin, followed by amination with 22 ethylene diamine or other polyamine.
23 .
24 Similarly, U.S. Patent No. 4,134,846, issued January 16, 19'19 to Machleder et al., discloses a fuel additive 26 composition comprising a mixture of (1) the reaction product 27 of an aliphatic hydrocarbon-substituted phenol, 2g epichlorohydrin and a primary or secondary mono- or 2g polyamine, and (2) a polyalkylene phenol. This.patent teaches that such compositions show excellent carburetor, 31 induction system and combustion chamber detergency and, in 32 addition, provide effective rust inhibition when used in 33 hydrocarbon fuels at low concentrations.

WO 97/43360 PCT/US97/0799!

O1 wino phenols are also known to function as 02 detergents/dispersants, antioxidants and anti-corrosion ~ 03 agents when used in fuel compositions. U.S. Patent 04 No. 4,320,021, issued March 16, 1982 to R. M. Lange, for z 05 example, discloses amino phenols having at least one 06 substantially saturated hydrocarbon-based substituent of at 07 least 30 carbon atoms. The amino phenols of this patent are Og taught to impart useful and desirable properties to Og oil-based lubricants and normally liquid fuels.
11 In addition, polybutlyamines have been taught to be useful 12 for preventing deposits in the intake system of internal 13 combustion engines. For example, U.S. Patent No. 4,832,702, 14 issued May 23, 1989 to Kummer et al., discloses fuel and lubricant compositions containing polybutly or 16 Poiyisobutylamine additives prepared by hydroformulating a 17 polybutene or polyisobutene and then subjecting the 1g resulting oxo product to a Mannich reaction or amination 19 under hydrogenating conditions.
21 Polyether amine fuel additives are also well known in the 22 art for the prevention and control of engine deposits.
23 These polyether additives have a polyoxyalkylene "backbone", 24 i.e., the polyether portion of the molecule consists of repeating oxyalkylene units. U.S. Patent No. 4,191,537, 26 issued March 4, 1980 to Lewis et al., for example, discloses 27 a fuel composition comprising a major portion of 2g hydrocarbons boiling in the gasoline range and from 30 to 2g 2,000 ppm of a hydrocarbyl polyoxyalkylene aminocarbamate having a molecular weight from about 600 to 10,000, and at 31 least one basic nitrogen atom. The hydrocarbyl 32 polyoxyalkylene moiety is composed of oxyalkylene units 33 having from 2 to 5 carbon atoms in each oxyalkylene unit.
34 These fuel compositions are taught to maintain the O1 cleanliness of intake systems without contributing to 02 combustion chamber deposits.

04 Aromatic compounds containing a poly(oxyalkylene) moiety are 05 also known in the art. For example, the above-mentioned U.S.
06 Patent No. 4,191,537, discloses alkylphenyl 07 poly(oxyalkylene) polymers which are useful as intermediates Og in the preparation of alkylphenyl poly(oxyalkylene) Og aminocarbamates.
11 Similarly, U.S. Patent No. 4,881,945, issued November 21, 12 1989 to Buckley, discloses a fuel composition comprising a 13 hydrocarbon boiling in the gasoline or diesel range and from 14 about 3o to about 5,000 parts per million of a fuel soluble alkylphenyl polyoxyalkylene aminocarbamate having at least 16 one basic nitrogen and an average molecular weight of about 17 800 to 6,000 and wherein the alkyl group contains at least 1g 40 carbon atoms.

U.S. Patent No. 5,112,364, issued May 12, 1992 to Rath et 21 al., discloses gasoline-engine fuels which contain small 22 amounts of a polyetheramine and/or a polyetheramine 23 derivative, wherein the polyetheramine is prepared by 24 reductive amination of a phenol-initiated or alkylphenol-initiated polyether alcohol with ammonia or a primary amine.

27 European Patent Application Publication No. 310,875, 2g published April 12, 1989 discloses fuels for spark ignition 2g engines containing a polyetheramine additive prepared by first propoxylating and/or butoxylating an alkanol or 31 primary or secondary alkylmonoamine and then aminating the 32 resulting polyether with ammonia or a primary aliphatic 33 amine.

01 French Patent No. 2,105,539, published April 28, 1972, 02 discloses carburetor detergent additives which are 03 phenoxypropylamines which may be substituted with up to five 04 hydrocarbon radicals of 1 to 30 carbon atoms on the aromatic 05 ring. This patent also discloses additives obtained by 06 reacting such phenoxypropylamines with alkylphosphoric 07 acids.

Og SUNadARY OF THE INVENTTON
il I have now discovered certain polyalkylphenoxyaminoalkanes 12 which provide excellent control of engine deposits, 13 especially intake valve deposits, when employed as fuel 14 additives in fuel compositions.
16 The compounds of the present invention include those having 17 the following formula and fuel soluble salts thereof:

, i 1 ~2 21 R O-CH-CH-A (I) 23 .
24 wherein R is a polyalkyl group having an average molecular weight in the range of about 600 to 5,000;

27 Rl and R2 are independently hydrogen or lower alkyl having 1 2g to 6 carbon atoms; and A is amino, N-alkyl amino having about 1 to about 20 carbon 31 atoms in the alkyl group, N,N-dialkyl amino having about 1 ' 32 to about 20 carbon atoms in each alkyl group, or a polyamine 33 moiety having about 2 to about 12 amine nitrogen atoms and ' 34 about 2 to about 40 carbon atoms.

01 The present invention further provides a fuel composition 02 comprising a major amount of hydrocarbons boiling in the 03 gasoline or diesel range and a deposit-controlling effective 04 amount of a compound of the present invention.

06 The present invention additionally provides a fuel 07 concentrate comprising an inert stable oleophilic organic Og solvent boiling in the range of from about 150°F. to 400°F.
p9 and from about 10 to 70 weight percent of a compound of the present invention.

Z2 Among other factors, the present invention is 13 based on the surprising discovery that certain 14 polyalkylphenoxyaminoalkanes provide excellent y5 control of engine deposits, especially on intake valves, 16 when employed as additives in fuel compositions.

The polyalkylphenoxyaminoalkanes of the present invention 21 have the general formula:

23 ~ f z i2 24 R O-CH-CH-A (I) 27 wherein R, R~, R2 and A are as defined above.

29 preferably, R is a polyalkyl group having an average molecular weight in the range of about 600 to 3,000, more 31 preferably about 700 to 3,000, and most preferably about 900 32 to 2,500.

WO 97!43360 PCT/US97/0799I
O1 ~'referably, one of R2 and RZ is hydrogen or lower alkyl of 1 02 to 4 carbon atoms, and the other is hydrogen. More - 03 preferably, one of Rl and R2 is hydrogen, methyl or ethyl, 04 and the other is hydrogen. Most preferably, R2 is hydrogen, 05 methyl or ethyl, and Rl is hydrogen.

07 In general, A is amino, N-alkyl amino having from about 1 to Og about 20 carbon atoms in the alkyl group, preferably about 1 Og to about 6 carbon atoms, more preferably about 1 to about 4 carbon atoms; N,N-dialkyl amino having from about 1 to about 11 20 carbon atoms in each alkyl group, preferably about 1 to 12 about 6 carbon atoms, more preferably about 1 to about 4 13 carbon atoms; or a polyamine moiety having from about 2 to 14 about 12 amine nitrogen atoms and from about 2 to about 40 carbon atoms, preferably about 2 to 12 amine nitrogen atoms 16 and about 2 to 24 carbon atoms. More preferably, A is amino 17 or a polyamine moiety derived from a polyalkylene polyamine, lg including alkylene diamine. Most preferably, A is amino or 19 a polyamine moiety derived from ethylene diamine or diethylene triamine.

22 It is preferred that the R substituent is located at the 23 mete or, more preferably, the pare position on the aromatic 24 ring, i.e., pare or mete relative to the ether group.
26 The compounds of the present invention will generally have a 27 sufficient molecular weight so as to be non-volatile at 2g normal engine intake valve operating temperatures (about 29 200°-250°C.). Typically, the molecular weight of the compounds of this invention will range from about 70o to 31 about 3,500, preferably from about 700 to about 2,500.

_g_ O1 Fuel-soluble salts of the compounds of formula I can be 02 readily prepared for those compounds containing an amino or 03 substituted amino group and such salts are contemplated to , 04 be useful for preventing or controlling engine deposits.
05 Suitable salts include, for example, those obtained by 06 protonating the amino moiety with a strong organic acid, p7 such as an alkyl- or arylsulfonic acid. Preferred salts are Og derived from toluenesulfonic acid and methanesulfonic acid.

Definitions 12 As used herein, the following terms have the following 13 meanings unless expressly stated to the contrary.

The term "amino" refers to the group: -NH2.

17 The term "N-alkylamino" refers to the group: -NHRa wherein lg Ra is an alkyl group. The term "N,N-dialkylamino'° refers to 19 the group: -ilRbR~, wherein Rb and R~ are alkyl groups.
21 The term "hydrocarbyl" refers to an organic radical 22 primarily composed of carbon and hydrogen which may be 23 aliphatic, alicyclic, aromatic or combinations thereof, 24 e.g., aralkyl or alkaryl. Such hydrocarbyl groups are generally free of aliphatic unsaturation, i.e., olefinic or 26 acetylenic unsaturation, but may contain minor amounts of 27 heteroatoms, such as oxygen or nitrogen, or halogens, such 28 as chlorine.

The term '°alkyl" refers to both straight- and branched-chain 31 alkyl groups.

01 The term "lower alkyl" refers to alkyl groups having 1 to 02 about 6 carbon atoms and includes primary, secondary and 03 tertiary alkyl groups. Typical lower alkyl groups include, 04 for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, 05 sec-butyl, t-butyl, n-pentyl, n-hexyl and the like.

The term "polyalkyl" refers to an alkyl group which is Og generally derived from polyolefins which are polymers or Og copolymers of mono-olefins, particularly 1-mono-olefins, lp such as ethylene, propylene, butylene, and the like.
11 Preferably, the mono-olefin employed will have 2 to about 12 24 carbon atoms, and more preferably, about 3 to 12 carbon 13 atoms. More preferred mono-olefins include propylene, 14 butyiene, particularly isobutylene, 1-octene and 1-decene.
15 Polyolefins prepared from such mono-olefins include 16 polypropylene, polybutene, especially polyisobutene, and the 1~ polyalphaolefins produced from 1-octene and 1-decene.

lg The term "fuel" or "hydrocarbon fuel" refers to normally 20 liquid hydrocarbons having boiling points in the range of 21 gasoline and diesel fuels.

23 General Synthetic Procedures 25 The polyalkylphenoxyaminoalkanes of this invention may be 26 prepared by the following general methods and procedures.
2~ It should be appreciated that where typical or preferred 2g process conditions (e. g., reaction temperatures, times, mole 2g ratios of reactants, solvents, pressures, etc.}. are given, 30 other process conditions may also be used unless otherwise 31 stated. Optimum reaction conditions may vary with the 32 particular reactants or solvents used, but such conditions 33 can be determined by one skilled in the art by routine ' 34 optimization procedures.

O1 Those skilled in the art will also recognize that it may be 02 necessary to block or protect certain functional groups 03 while conducting the following synthetic procedures. In 04 such cases, the protecting group will serve to protect the 05 functional group from undesired reactions or to block its 06 undesired reaction with other functional groups or with the 07 reagents used to carry out the desired chemical Og transformations. The proper choice of a protecting group O9 for a particular functional group will be readily apparent to one skilled in the art. Various protecting groups and 11 their introduction and removal are described, for example, 12 in T. W. Greene and P. G. M. Wuts, Protective Groups in 13 Organic Synthesis, Second Edition, Wiley, New York, 1991, 14 and references cited therein.
16 Synthesis lg The polyalkylphenoxyaminoalkanes of the present invention lg may be prepared by a process which initially involves hydroxyalkylation of a polyalkylphenol of the formula:

23 . R OH (II) 26 wherein R is as defined herein, with an alkylene carbonate 2~ of the formula:

O

31 (III) 33 Rl R2 WO 97!43360 PCT/US97l07991 O1 wherein Rl and RZ
are as defined herein, in the presence of 02 a catalytic amount of an alkali metal hydride or hydroxide, 03 or alkali metal salt, to provide a polyalkylphenoxyalkanol 04 of the formula:

_ 05 06 i 1 12 R O-C
C
O
IV

07 ) H-H-H ( wherein R, R1 and R2 are as defined herein.

The polyalkylphenols of formula II are well known materials and are typically prepared by the alkylation of phenol with the desired polyolefin or chlorinated polyolefin.
A further discussion of polyalkylphenols can be found, for example, in US. Patent No. 4,744,921 and U.S. Patent No. 5,300,701.

Accordingly, the polyalkylphenols of formula II may be prepared from the corresponding olefins by conventional procedures. For example, the polyalkylphenols of formula II

above may be prepared by reacting the appropriate olefin or olefin mixture with phenol in the presence of an alkylating catalyst at a temperature of from about 25C.
to 150C., and preferably 30C. to 100C. either neat or in an essentially inert solvent at atmospheric pressure.
A preferred alkylating catalyst is boron trifluoride.
Molar ratios of reactants may be used. Alternatively, molar excesses of phenol can be employed, i.e., 2 to 3 equivalents of phenol for each equivalent of olefin with unreacted phenol recycled. The latter process maximizes monoalkylphenol.

Examples of inert solvents include heptane, benzene, toluene, chlorobenzene and 250 thinner which is a mixture of aromatics, paraffins and naphthenes.

1 The polyalkyl substituent on the polyalkylphenols employed in 2 the invention is generally derived from polyolefins which are 3 polymers or copolymers of mono-olefins, particularly 1-mono-4 olefins, such as ethylene, propylene, butylene, and the like.
Preferably, the mono-olefin employed will have 2 to about 24 6 carbon atoms, and more preferably, about 3 to 12 carbon atoms.

7 More preferred mono-olefins include propylene, butylene, 8 particularly isobutylene, 1-octene and 1-decene. Polyolefins 9 prepared from such mono-olefins include polypropylene, polybutene, especially polyisobutene, and the polyalphaolefins 11 produced from 1-octene and 1-decene.

13 The preferred polyisobutenes used to prepare the presently 14 employed polyalkylphenols are polyisobutenes which comprise at least about 20% of the more reactive methylvinylidene isomer, 16 preferably at least 50% and more preferably at least 70%.
17 Suitable polyisobutenes include those prepared using BF3 18 catalysts. The preparation of such polyisobutenes in which the 19 methylvinylidene isomer comprises a high percentage of the total composition is described in U.S. Patent Nos. 4,152,499 21 and 4,605,808. Such polyisobutenes, known as "reactive"
22 polyisobutenes, yield high molecular weight alcohols in which 23 the hydroxyl group is at or near the end of the hydrocarbon 24 chain. Examples of suitable polyisobutenes having a high alkylvinylidene content include Ultravis 30, a polyisobutene 26 having a number average molecular weight of about 1300 and a 27 methylvinylidene content of about 74%, and UltravisTM 10, a 28 polyisobutene having a number average molecular weight of 29 about 950 and a methylvinylidene content of about 76%, both available from British Petroleum.

WO 97/43360 PCT/LTS97/0799!

01 The alkylene carbonates of formula III are known compounds 02 which are available commercially or can be readily prepared 03 using conventional procedures. Suitable alkylene carbonates 04 include ethylene carbonate, propylene carbonate, 1,2-05 butylene carbonate, 2,3-butylene carbonate, and the like. A
06 preferred alkylene carbonate is ethylene carbonate.

Og The catalyst employed in the reaction of the polyaklyphenol Og and alkylene carbonate may be any of the well known hydroxyalkylation catalysts. Typical hydroxyalkylation 11 catalysts include alkali metal hydrides, such as lithium 12 hydride, sodium hydride and potassium hydride, alkali metal 13 hydroxides, such as sodium hydroxide and potassium 14 hydroxide, and alkali metal salts, for example, alkali metal halides, such as sodium chloride and potassium chloride, and 16 alkali metal carbonates, such as sodium carbonate and 17 potassium carbonate. The amount of catalyst employed will lg generally range from about 0.01 to 1.0 equivalent, 1g. preferably from about 0.05 to 0.3 equivalent.
21 The polyalkylphenol and alkylene carbonate are generally 22 reacted in essentially equivalent amounts in the presence of 23 the hydroxyalkylation catalyst at a temperature in the range 24 of about 100°C. to 210°C., and preferably from about 150°C.
to about 170°C. The reaction may take place in the presence 26 or absence of an inert solvent.

2g The time of reaction will vary depending on the particular 2g alkylphenol and alkylene carbonate reactants, the catalyst used and the reaction temperature. Generally, the reaction 31 time will range from about two hours to about five hours.
32 The progress of the reaction is typically monitored by the 33 evolution of carbon dioxide. At the completion of the O1 reaction, the polyalkylphenoxyalkanol product is isolated 02 using conventional techniques.
03 _ 04 The hydroxyalkylation reaction of phenols with alkylene 05 carbonates is well known in the art and is described, for -06 example, in U.S. Patent Nos. 2,987,555; 2,967,892; 3,283,030 and 4,341,905.
OS
Og Alternatively, the polyalkylphenoxyalkanol product of formula IV may be prepared by reacting the polyalkylphenol 11 of formula II with an alkylene oxide of the formula:

13 ~O

R1-CH CH-R2 (V) 1~ wherein R1 and R2 are as defined herein, in the presence of ig a hydroxyalkylation catalyst as described above.

Suitable alkylene oxides of formula V include ethylene 21 oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene 22 oxide, and the like. A preferred alkylene oxide is ethylene 23 oxide.

In a manner similar to the reaction with alkylene carbonate, 26 the polyalkylphenol and alkylene oxide are reacted in 2-7 essentially equivalent or equimolar amounts in the presence 2g of 0.01 to 1.0 equivalent of a hydroxyalkylation catalyst, 2g such as sodium or potassium hydride, at a temperature in the range of about 30°C. to about 150°C., for about 2 to about 31 24 hours. The reaction may be conducted in the presence or 32 absence of a substantially anhydrous inert solvent. ' 33 Suitable solvents include toluene, xylene, and the like.
34 Generally, the reaction is conducted at a pressure O1 sufficient to contain the reactants and any solvent present, 02 typically at atmospheric or higher pressure. Upon 03 completion of the reaction, the polyalkylphenoxyalkanol is 04 isolated by conventional procedures.

06 The polyalkylphenoxyalkanol of formula IV is subsequently 07 reacted, either directly or through an intermediate, with an Og appropriate amine to provide the desired Og polyalkylphenoxyaminoalkanes of formula T. Suitable amine reactants which may be employed to form the amine component, 11 i.e., substituent A, of the polyalkylphenoxyaminoalkanes of 12 the present invention are discussed more fully below.

lg The Amine Component 16 In general, the amine component of the present 17 polyalkylphenoxyaminoalkanes will contain an average of at lg least about one basic nitrogen atom per molecule. A "basic 19 nitrogen atom" is one that is titratable by a strong acid, for example, a primary, secondary, or tertiary amine 21 nitrogen; as distinguished from, for example, an carbamyl 22 nitrogen, e.g., -OC(O)NH-, which is not titratable with a 23 strong acid. Preferably, at least one of the basic nitrogen 24 atoms of the amine component will be primary or secondary amine nitrogen, more preferably, at least one will be a 26 primary amine nitrogen.

2g The amine component of the polyalkylphenoxyaminoalkanes of 2g this invention is preferably derived from ammonia, a primary alkyl or secondary dialkyl monoamine, or a polyamine having 31 a terminal amino nitrogen atom.

33 Primary alkyl monoamines useful in preparing compounds of ' 34 the present invention contain 1 nitrogen atom and from about O1 1 to about 20 carbon atoms, more preferably about 1 to 6 02 carbon atoms, most preferably 1 to 4 carbon atoms. Examples 03 of suitable monoamines include N-methylamine, N-ethylamine, 04 N-n-propylamine, N-isopropylamine, N-n-butylamine, N-05 isobutylamine, N-sec-butylamine, N-tert-butylamine, N-n-06 pentylamine, N-cyclopentylamine, N-n-hexylamine, N-O~ cyclohexylamine, N-octylamine, N-decylamine, N-dodecylamine, pg N-octadecylamine, N-benzylamine, N-(2-phenylethyl)amine, 2-Og aminoethanol, 3-amino-1-propanol, 2-(2-aminoethoxy)ethanol, N-(2-methoxyethyl)amine, N-(2-ethoxyethyl)amine and the i1 like. Preferred primary amines are N-methylamine, 12 N-ethylamine and N-n-propylamine.

14 The amine component of the present polyalkylphenoxyaminoalkanes may also be derived from a 16 secondary dialkyl monoamine. The alkyl groups of the 1~ secondary amine may be the same or different and will lg generally each contain about 1 to about 20 carbon atoms, ig more preferably about 1 to about 6 carbon atoms, most preferably about 1 to about 4 carbon atoms. One or both of 21 the alkyl groups may also contain one or more oxygen atoms.

23 Preferably, the alkyl groups of the secondary amine are 24 independently selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, 2-hydroxyethyl and 2-26 methoxyethyl. More preferably, the alkyl groups are methyl, 2~ ethyl or propyl.

2g Typical secondary amines which may be used in this invention include N,N-dimethylamine, N,N-diethylamine, N,N-di-n-31 propylamine, N,N-diisopropylamine, N,N-di-n-butylamine, 32 N,N-di-sec-butylamine, N,N-di-n-pentylamine, N,N-di-n- "
33 hexylamine, N,N-dicyclohexylamine, N,N-dioctylamine, 34 N-ethyl-N-methylamine, N-methyl-N-n-propylamine, N-n-butyl- -01 N-methylamine, N-methyl-N-octylamine, N-ethyl-N-02 isopropylamine, N-ethyl-N-octylamine, N,N-di(2-03 hydroxyethyl)amine, N,N-di(3-hydroxypropyl)amine, 04 N,N-di(ethoxyethyl)amine, N,N-di(propoxyethyl)amine and the . 05 like. Preferred secondary amines are N,N-dimethylamine, 06 N,N-diethylamine and N,N-di-n-propylamine.

pg Cyclic secondary amines may also be employed to form the Og additives of this invention. In such cyclic compounds, the alkyl groups, when taken together, form one or more 5- or 12 6-membered rings containing up to about 20 carbon atoms.
12 The ring containing the amine nitrogen atom is generally 13 saturated, but may be fused to one or more saturated or 14 unsaturated rings. The rings may be substituted with hydrocarbyl groups of from 1 to about 10 carbon atoms and 16 may contain one or more oxygen atoms.

1g Suitable cyclic secondary amines include piperidine, 19 4-methylpiperidine, pyrrolidine, morpholine, 2,6-dimethylmorpholine and the like.

22 Suitable polyamines can have a straight- or branched-chain 23 structure and may be cyclic or acyclic or combinations 24 thereof. Generally, the amine nitrogen atoms of such polyamines will be separated from one another by at least 26 two carbon atoms, i.e., polyamines having an aminal 2~ structure are not suitable. The polyamine may also contain 2g one or more oxygen atoms, typically present as an ether or a 2g hydroxyl group. Polyamines having a carbon-to-nitrogen ratio of from about 1:1 to about 10:1 are particularly preferred.

' 32 In preparing the compounds of this invention using a 33 polyamine where the various nitrogen atoms of the polyamine 34 are not geometrically equivalent, several substitutional WO 97!43360 PCT/LTS97/0799I

O1 isomers are possible and each of these possible isomers is 02 encompassed within this invention.
03 _ 04 A particularly preferred group of polyamines for use in the 05 present invention are polyalkylene polyamines, including 06 alkylene diamines. Such polyalkylene polyamines will 07 typically contain from about 2 to about 12 nitrogen atoms 08 and from about 2 to about 40 carbon atoms, preferably about Og 2 to 24 carbon atoms. Preferably, the alkylene groups of such polyalkylene polyamines will contain from about 2 to 11 about 6 carbon atoms, more preferably from about 2 to about 12 4 carbon atoms.

14 examples of suitable polyalkylene polyamines include ethylenediamine, propylenediamine, isopropylenediamine, 16 butylenediamine, pentylenediamine, hexylenediamine, 17 diethylenetriamine, dipropylenetriamine, lg dimethylaminopropylamine, diisopropylenetriamine, lg dibutylenetriamine, di-sec-butylenetriamine, triethylenetetraamine, tripropylenetetraamine, 21 triisobutylenetetraamine, tetraethylenepentamine, 22 pentaethylenehexamine, dimethylaminopropylamine, and 23 mixtures thereof..

Particularly suitable polyalkylene polyamines are those 26 having the formula:

28 H2N-(Rg-NH)Z-H

wherein Rg is a straight- or branched-chain alkylene group 31 having from about 2 to about 6 carbon atoms, preferably from 32 about 2 to about 4 carbon atoms, most preferably about 2 -33 carbon atoms, i.e., ethylene {-CH2CH2-); and z is an integer 34 from about 1 to about 4, preferably about 1 or about 2. -O1 Particularly preferred polyalkylene polyamines are 02 ethylenediamine, diethylenetriamine, triethylenetetraamine, 03 and tetraethylenepentamine. Most preferred are 04 ethylenediamine and diethylenetriamine, especially 05 ethylenediamine.

07 Also contemplated for use in the present invention are Og cyclic polyamines having one or more 5- to 6-membered rings.
Og Such cyclic polyamines compounds include piperazine, 2-methylpiperazine, N-(2-aminoethyl)piperazine, 11 N-(2-hydroxyethyl)piperazine, 1,2-bis-(N-piperazinyl)ethane, 12 3-aminopyrrolidine, N-(2-aminoethyl)pyrrolidine, and the 13 like. Among the cyclic polyamines, the piperazines are 14 preferred.
16 Many of the polyamines suitable for use in the present 17 invention are commercially available and others may be 1g prepared by methods which are well known in the art. For 1g example, methods for preparing amines and their reactions are detailed in Sidgewick's 'The Organic Chemistry of 21 Nitrogen", Clarendon Press, Oxford, 1966; Noller's 22 "Chemistry of Organic Compounds", Saunders, Philadelphia, 23 2nd Ed., 1957; and Kirk-Othmer's "Encyclopedia of Chemical 24 Technology", 2nd Ed., especially Volume 2, pp. 99-116.
26 Preparation of the Polyalkylphenoxyaminoalkane 2g As noted above, the polyalkylphenoxyaminoalkanes of the 2g present invention may be conveniently prepared by reacting the polyalkylphenoxyalkanol of formula IV, either directly 31 or through an intermediate, with a nitrogen-containing ' 32 compound, such as ammonia, a primary or secondary alkyl 33 monoamine, or a polyamine, as described herein.
' 34 1 Accordingly, the polyalkylphenoxyalkanol of formula IV may be 2 converted to the desired polyalkylphenoxyaminoalkane by a 3 variety of procedures known in the art.

For example, the terminal hydroxy group on the 6 polyalkylphenoxyalkanol may first be converted to a suitable 7 leaving group, such as a mesylate, chloride or bromide, and 8 the like, by reaction with a suitable reagent, such as 9 methanesulfonyl chloride. The resulting polyalkylphenoxyalkyl mesylate or equivalent intermediate may then be converted to a 11 phthalimide derivative by reaction with potassium phthalimide 12 in the presence of a suitable solvent, such as N,N-13 dimethylforamide. The polyalkylphenoxyalkyl phthalimide 14 derivative is subsequently converted to the desired polyalkylphenoxyaminoalkane by reaction with a suitable amine, 16 such as hydrazine. Alternatively, the leaving group can be 17 converted to an azide, as described, for example, in Turnbull 18 Scriven, Chemical Reviews, Volume 88, pages 297-368, 1988. The 19 azide is subsequently converted to the desired polyalkylphenoxyaminoalkane by reduction with hydrogen and a 21 catalyst, such as palladium on carbon or a Lindlar catalyst.

23 The polyalkylphenoxyalkanol of formula IV may also be 24 converted to the corresponding polyyalkylphenoxyalkyl chloride by reaction with a suitable halogenating agent, such as HCl, 26 thionyl chloride, or epichlorohydrin, followed by displacement 27 of the chloride with a suitable amine, such as ammonia, a 28 primary or secondary alkyl monoamine, or a polyamine, as 29 described, for example, in U.S. Patent No. 4,247,301 to Honnen.

, CA 02226982 2005-11-28 1 Alternatively, the polyalkylphenoxyaminoalkanes of the 2 present invention may be prepared from the corresponding 3 polyalkylphenoxyalkanol by a process commonly referred to 4 as reductive amination, such as described in U.S. Patent No. 5,112,364 to Rath et al. and U.S. Patent No.
6 4,332,595 to Herbstman et al.

8 In the reductive amination procedure, the 9 polyalkylphenoxyalkanol is aminated with an appropriate amine, such as ammonia or a primary alkyl monoamine, in 11 the presence of hydrogen and a hydrogenation-12 dehydrogenation catalyst. The amination reaction is 13 typically carried out at temperatures in the range of 14 about 160°C to about 250°C and pressures of about 1,000 to about 5,000 psig, preferably about 1,500 to about 3,000 16 psig. Suitable hydrogenation-dehydrogenation catalysts 17 include those containing platinum, palladium, cobalt, 18 nickel, copper, or chromium, or mixtures thereof.
19 Generally, an excess of the ammonia or amine reactant is used, such as about a 5-fold to about 60-fold molar 21 excess, and preferably about a 10-fold to about 40-fold 22 molar excess, of ammonia or amine.

24 When the reductive amination is carried out with a polyamine reactant, the amination is preferably conducted 26 using a two-step procedure as described in commonly-27 assigned copending European Patent Application No.
28 0781793 and titled "Reductive Amination Process for 29 Manufacturing a Fuel Additive From Polyoxybutylene Alcohol with Ethylene Diamine". According to this 31 procedure, an appropriate alcohol is first contacted with 32 a hydrogenation-dehydrogenation catalyst at a temperature 33 of at least 230°C to provide a carbonyl-WO 97!43360 PCTILTS97/0799!

01 containing intermediate, which is subsequently reacted with 02 a polyamine at a temperature below about 190°C in the 03 presence of hydrogen and a hydrogenation catalyst to produce 04 the desired polyamine adduct.

06 In an alternative procedure for preparing the 07 polyalkylphenoxyaminoalkanes of the present invention, the Og polyalkylphenol of formula II may be reacted with an Og aziridine of the formula:

R1-CH- H-R2 (VI) 16 wherein RI and R2 are as defined herein, and R4 is hydrogen 17 or alkyl of 1 to 20 carbon atoms. A preferred aziridine is 18 one wherein R~ is hydrogen, R2 is hydrogen, methyl or ethyl, 19 and R4 is hydrogen.
21 The reaction of aziridines with alcohols to produce beta-22 amino ethers is well known in the art and is discussed, for 23 example, in Ham and Dermer, "Ethyleneimine and Other 24 Aziridines", Academia Press, New York, 1969, pages 224-227 and 256-257.

27 Fuel Compositions 29 The compounds of the present invention are useful as additives in hydrocarbon fuels to prevent and control engine 31 deposits, particularly intake valve deposits. The proper 32 concentration of additive necessary to achieve the desired -33 deposit control varies depending upon the type of fuel WO 97/43360 PCT/CTS97l07991 01 employed, the type of engine, and the presence of other fuel 02 additives.

04 In general, the concentration of the compounds of this 05 invention in hydrocarbon fuel will range from about 50 to ~ 06 about 2500 parts per million (ppm) by weight, preferably 07 from 75 to 1,000 ppm. When other deposit control additives Og are present, a lesser amount of the present additive may be Og used.
11 The compounds of the present invention may be formulated as 12 a concentrate using an inert stable oleophilic (i.e., 13 dissolves in gasoline) organic solvent boiling in the range 14 of about 150°F. to 400°F. (about 65°C. to 205°C.).
Preferably, an aliphatic or an aromatic hydrocarbon solvent 16 is used, such as benzene, toluene, xylene or higher-boiling 17 aromatics or aromatic thinners. Aliphatic alcohols 1g containing about 3 to 8 carbon atoms, such as isopropanol, 1g isobutylcarbinol, n-butanol and the like, in combination with hydrocarbon solvents are also suitable for use with the 21 present additives. Tn the concentrate, the amount of the 22 additive will generally range from about 10 to about 23 70 weight percent, preferably 10 to 50 weight percent, more 24 preferably from 20 to 40 weight percent.
in gasoline fuels, other fuel additives may be employed with 26 the additives of the present invention, including, for 27 example, oxygenates, such as t-butyl methyl ether, antiknock 2g agents, such as methylcyclopentadienyl manganese 2g tricarbonyl, and other dispersants/detergents, such as hydrocarbyl amines, hydrocarbyl poly(oxyalkylene) amines, 31 hydrocarbyl poly(oxyalkylene) aminocarbamates, or - 32 succinimides. Additionally, antioxidants, metal 33 deactivators and demulsifiers may be present.
~ 34 01 In diesel fuels, other well-known additives can be employed, 02 such as pour point depressants, flow improvers, cetane 03 improvers, and the like.

05 A fuel-soluble, nonvolatile carrier fluid or oil may also be , 06 used with the compounds of this invention. The carrier 07 fluid is a chemically inert hydrocarbon-soluble liquid Og vehicle which substantially increases the nonvolatile Og residue (NVR), or solvent-free liquid fraction of the fuel additive composition while not overwhelmingly contributing 11 to octane requirement increase. The carrier fluid may be a 12 natural or synthetic oil, such as mineral oil, refined 13 petroleum oils, synthetic polyalkanes and alkenes, including 14 hydrogenated and unhydrogenated polyalphaolefins, and synthetic polyoxyalkylene-derived oils, such as those 16 described, for example, in U.S. Patent No. 4,191,537 to 17 Lewis, and polyesters, such as those described, for example, ig in U.S. Patent Nos. 3,756,793 to Robinson and 5,004,478 to ig Vogel et al., and in European Patent Application Nos. 356,726, published March 7, 1990, and 382,159, 21 published August 16, 1990.

23 These carrier fluids are believed to act as a carrier for 24 the fuel additives of the present invention and to assist in removing and retarding deposits. The carrier fluid may also 26 exhibit synergistic deposit control properties when used in 27 combination with a compound of this invention.

29 The carrier fluids are typically employed in amounts ranging from about 100 to about 5000 ppm by weight of the 31 hydrocarbon fuel, preferably from 400 to 3000 ppm of the 32 fuel. Preferably, the ratio of carrier fluid to deposit 33 control additive will range from about 0.5:1 to about lo: l, 34 more preferably from 1:1 to 4:1, most preferably about 2:1. ' O1 When employed in a fuel concentrate, carrier fluids will 02 generally be present in amounts ranging from about 2o to - 03 about 60 weight percent, preferably from 30 to 50 weight 04 percent.

Og A further understanding of the invention can be had in the 09 following nonlimiting Examples. Wherein unless expressly stated to the contrary, all temperatures and temperature 11 ranges refer to the Centigrade system and the term "ambient"
12 or "room temperature" refers to about 20°C.-25°C. The term 13 "percent" or "%" refers to weight percent and the term 14 "mole" or "moles" refers to gram moles. The term "equivalent" refers to a quantity of reagent equal in moles, 16 to the moles of the preceding or succeeding reactant recited 17 in that example in terms of finite moles or finite weight or lg volume. Where given, proton-magnetic resonance spectrum 19 (p~m~r. or n.m.r.) were determined at 300 mHz, signals are assigned as singlets (s), broad singlets (bs), doublets (d), 21 double doublets (dd), triplets (t), double triplets (dt), 22 quartets (q), and multiplets (m), and cps refers to cycles 23 per second.

Example 1 27 Preparation of Polyisobutyl Phenol 2g To a flask equipped with a magnetic stirrer, reflux condenser, thermometer, addition funnel and nitrogen inlet 31 was added 203.2 grams of phenol. The phenol was warmed to 32 40°C. and the heat source was removed. Then, 73.5 ' 34 WO 97!43360 PCT/LTS97/0799I

O1 milliliters of boron trifluoride etherate was added O2 dropwise. 1040 grams of Ultravis 10 Polyisobutene 03 (molecular weight 950, 76% methylvinylidene, available from 04 British Petroleum) was dissolved in 1,863 milliliters of 05 hexane. The polyisobutene was added to the reaction at a 06 rate to maintain the temperature between 22°C-27°C. The 07 reaction mixture was stirred far 16 hours at room 08 temperature. Then, 400 milliliters of concentrated ammonium 09 hydroxide was added, followed by 2,000 milliliters of to hexane. The reaction mixture was washed with water (3 X
21 2,000 milliliters), dried over magnesium sulfate, filtered 12 and the solvents removed under vacuum to yield 1,056.5 grams 13 of a crude reaction product. The crude reaction product was 14 determined to contain 80% of the desired product by proton 15 NMR and chromatography on silica gel eluting with hexane, 16 followed by hexane: ethylacetate: ethanol (93:5:2).

18 Example 2 20 Preparation of 2 2 ~~H

2~ P1B {molecular weight - 950) Potassium hydride (1.1 grams of a 35 weight percent dispersion of in mineral oil) and 4- polyisobutyl phenol 32 (9g'7 grams, prepared as in Example 1) were added to a , flask equipped with a magnetic stirrer, reflux condensor, nitrogen inlet and thermometer. The reaction was heated at O1 130°C for one hour and then cooled to 100°C. Ethylene 02 carbonate (8.6 grams) was added and the mixture was heated 03 at 160°C far 16 hours. The reaction was cooled to room 04 temperature and one milliliter of isopropanol was added.
05 The reaction was diluted with one liter of hexane, washed three times with water and once with brine. The organic 07 layer was dried over anhydrous magnesium sulfate, filtered Og and the solvents removed in vacuo to yield 98.0 grams of the Og desired product as a yellow oil.
to 11 Example 3 13 Preparation of 15 O~~S ~2C H3 2 0 P IB (molecular weight ~ 950) The alcohol from Example 2 (20.0 grams), triethylamine (2.9 mL), and anhydrous dichloromethane (200 mL) were combined.

The solution was cooled to 0°C and methanesulfonyl chloride (1.5 mL) was added dropwise. The reaction was stirred at room temperture under nitrogen for 16 hours. The solution was diluted with dichloromethane (600 mL) and was washed twice with saturated aqueous sodium bicarbonate solution and once with brine. The organic layer was dried over anhydrous sodium sulfate, filtered and the solvents removed in vacuo to yield 20.4 grams as a yellow oil.

WO 97/43360 PCT/CTS97/0799!
_2g_ O1 Example 4 03 Preparation of 06 O~N~NH2 o8 11 P IB (molecular weigf~t ~ 950) 13 Ethylenediamine (12.3 mL) and anhydrous toluene (100 mL) 14 were combined under nitrogen. The product from Example 3 (20.4 grams, dissolved in 100 mL of anhydrous toluene) was 16 added dropwise. The resulting solution was refluxed for 16 17 hours. The solution was diluted with hexane (600 mL) and was 18 washed once with saturated aqueous sodium bicarbonate 19 solution , three times with water and once with brine. The organic layer was dried over anhydrous sodium sulfate, 21 filtered and the solvents removed in vacuo to yield 15.3.
22 grams as a yellow oil. The oil was chromatographed on silica 23 gels eluting with~hexane / diethyl ether _(50:50) then hexane 24 / diethyl ether / methanol / isopropylamine ( 40:40:15:5) to yield 10.3 grams of the desired product as a yellow oil. 1H
26 ~ (CDCLg) d 7.25 (d, 2H), 6.8 {d, 2H), 4.1 (t, 2H), 3.0 27 (t, 2H), 2.85 (t, 2H), 2.75 {t, 2H ), 1.95 (bs, 3H), 1.5-0.7 28 {m~ 137H).

32 ' 34 ' O1 Example 5 03 Preparation of 06 O/~N3 11 P IB (molecular weight ~ 950) 13 A mesylate prepared as described in Example 3 (406.5 grams), 14 sodium azide (198.2 grams ), Adogen 464, a methyltrialltyl (C8_C~o) ammonium chloride available from Ashland Chemical 16 (g.p mL ), N,N - dimethyformamide (800 mL ) and toluene (1.2 17 L ) were combined. The reaction was refluxed for sixteen 18 hours and cooled to room temperature. The mixture was i9 filtered and the solvent was removed in vacuo . The residue was diluted with hexane (3.0 L ) and washed three times with 21 water and once with brine. The organic layer was dried over 22 anhydrous magnesium sulfate, filtered and the solvents 23 removed in vacuo to yield 334.3 grams of the desired azide 24 ~as a yellow oil.

01 Example 6 03 Preparation of o s O~NH2 os /

11 P IB (molecular weight ~ 950) 13 p, solution of the product from Example 5 ( 334.3 grams ) in 14 ethyl acetate (750 mL j and toluene (750 mL ), containing 10~ palladium on charcoal ( 7.0 grams j was hydrogenolyzed 16 at 35-40 psi for 16 hours on a Parr low pressure 17 hydrogenator. Catalyst filtration and removal of the 18 solvent in vacuo yielded 322.3 grams of the desired 19 product as a yellow oil. 1H NMR (CDClg) d 7.25 (d, 2H), 6.8 (d, 2H ), 4.0 (t, 1H), 3.1 (t, 2H), 2.35 (bs, 2Hj, 0.7-1.6 21 (m, 137H).

32 ' 34 ' O1 Examble 7 03 Preparation of to P IB (molecular weight ~ 950) Potassium hydride (15.1 grams of a 35 weight percent dispersion of in mineral oil) and 4- polyisobutyl phenol (1378.5 grams, prepared as in Example 1) were added to a flask equipped with a mechanical stirrer, reflux condensor, nitrogen inlet and thermometer. The reaction was heated at 130°C for one hour and then cooled to 100°C. Propylene carbonate (115.7 milliliters) was added and the mixture was heated at 160°C for 16 hours. The reaction was cooled to room temperature and ten milliliters of isopropanol were added. The reaction was diluted with ten liters of hexane, washed three times with water and once with brine. The organic layer was dried over anhydrous magnesium sulfate, filtered and the solvents removed in vacuo to yield 1301.7 grams of the desired product as a yellow oil.

' 34 01 Example 8 03 Pr~aration of 11 P IB (molecular weight ~ 950) 13 The alcohol from Example 7 (50.0 grams), triethylamine (7.0 14 mL), and anhydrous dichioromethane (500 mL) were combined.
The solution was cooled to 0°C and methanesulfonyl chloride 16 (3.7 mL) was added dropwise. The reaction was stirred at 17 room temperture under nitrogen for 16 hours. The solution 18 was diluted with dichloromethane (1.5L ) and was washed 19 three times with saturated aqueous sodium bicarbonate solution and once with brine. The organic layer was dried 21 over anhydrous sodium sulfate, filtered and the solvents 22 removed in vacuo to field 57.7 rams as a y g yellow oil.

O1 Example 9 O3 Preparation of Os 11 PiB (molecuia~weight ~ 950) 13 The mesylate from Example 8 (57.7 grams ), sodium azide 14 (27.1 grams ), Adogen 464 {1.0 mL ), N,N - dimethyformamide (400 mL ) and. toluene (600 mL ) were combined. The reaction 16 was refluxed for sixteen hours and cooled to room 17 temperature. The mixture was filtered and the solvent was 18 removed in vacuo . The residue was diluted with hexane (1.5 19 ~, ) and washed three times with water and once with brine.
The organic layer was dried over anhydrous magnesium 21 sulfate, filtered and the solvents removed in vacuo to yield 22 43.1 grams of the desired azide as a yellow oil.

1 Example 10 3 Preparation of 8 ~ ~
P ~ (molecular weight ~ 950) 11 A solution of the product from Example 9 ( 43.1 grams ) in 12 ethyl acetate (100 mL ) and toluene (100 mL ), containing 10%
13 palladium on charcoal ( 2.O grams ) was hydrogenolyzed at 35-14 40 psi for 16 hours on a Parr low pressure hydrogenator.
Catalyst filtration and removal of the solvent in vacuo 16 yielded 41.5 grams of the desired product as a yellow oil. 1H
17 NMR (CDC13) d 7.25 (d, 2H) , 6. 85 (d, 2H) , 3 .9 (abq, 1H) , 3 .65 18 (abq, 1H), 3.35 (m, 1H), 1.9 (bs, 2H), 0.7-1.6 (m, 140H).

Example 11 22 Single-Cylinder Engine Test 24 The test compounds were blended in gasoline and their deposit reducing capacity determined in an ASTM~CFR single-cylinder 26 engine test.

28 A WaukeshaT"" CFR single-cylinder engine was used. Each run was 29 carried out for 15 hours, at the end of which time the intake valve was removed, washed with hexane and weighed.

_35_ 01 The previously determined weight of the clean valve was 02 subtracted from the weight of the value at the end of the 03 run. The differences between the two weights is the weight 04 of the deposit. A lesser amount of deposit indicates a 05 superior additive. The operating conditions of the test 06 were as follows: water jacket temperature Zoo°F; vacuum of 07 12 in Hg, air-fuel ratio of 12, ignition spark timing of Og 400 BTC; engine speed is 1800 rpm; the crankcase oil is a Og commercial 30W oil.
11 The amount of carbonaceous deposit in milligrams on the 12 intake valves is reported for each of the test compounds in 13 Table I and Table II.

TABLE I

17 Intake Valve Deposit Weight 18 (in milligrams) 19 Sampler Run 1 Run 2 Average Base Fuel 333.5 354.9 344.2 21 Example 4 22.5 22.7 22.6 23 rAt 150 parts per million actives (ppma).

TABLE II

27 Intake Valve Deposit Weight 28 (in milligrams) 29 Sampler Run 1 Run 2 Average Base Fuel 323.8 312.1 318.0 31 Example 6 12.1 21.0 16.6 ' 32 33 rAt 125 parts per million actives (ppma).
' 34 WO 97!43360 PCT/US97/07992 01 The base fuel employed in the above single-cylinder engine O2 tests was a regular octane unleaded gasoline containing no 03 fuel detergent. The test compounds were admixed with the .
04 base fuel to give the concentrations indicated in the 05 tables.

07 The data in Table I and Table II illustrates the significant Og reduction in intake valve deposits provided by the Og polyalkylphenoxyaminoalkanes of the present invention (Examples 4 and 6) compared to the base fuel.

32 ' 34 '

Claims (63)

WHAT IS CLAIMED IS:

1. A compound of the formula:
or a fuel-soluble salt thereof, wherein R is a polyalkyl group having an average molecular weight in the range of about 600 to 5,000;
R1 and R2 are independently hydrogen or lower alkyl having 1 to 6 carbon atoms; and A is amino, N-alkyl amino having 1 to 20 carbon atoms in the alkyl group, N,N-dialkyl amino having 1 to 20 carbon atoms in each alkyl group, or a polyamine moiety having 2 to 12 amine nitrogen atoms and 2 to 40 carbon atoms.

2. The compound according to Claim 1, wherein one of R1 and R2 is hydrogen or lower alkyl of 1 to 4 carbon atoms, and the other is hydrogen.

3. The compound according to Claim 2, wherein one of R1 and R2 is hydrogen, methyl or ethyl, and the other is hydrogen.

4. The compound according to Claim 3, wherein R2 is hydrogen, methyl or ethyl, and R1 is hydrogen.

5. The compound according to Claim 1, wherein R is a polyalkyl group having an average molecular weight in the range of about 600 to 3,000.

6. The compound according to Claim 5, wherein R is a polyalkyl group having an average molecular weight in the range of about 700 to 3,000.

7. The compound according to Claim 6, wherein R is a polyalkyl group having an average molecular weight in the range of about 900 to 2,500.

8. The compound according to Claim 1, wherein R is a polyalkyl group derived from polypropylene, polybutene, or a polyalphaolefin oligomer of 1-octene or 1-decene.

9. The compound according to Claim 8, wherein R is a polyalkyl group derived from polyisobutene.

10. The compound according to Claim 9, wherein the polyisobutene contains at least about 20% of a methylvinylidene isomer.

11. The compound according to Claim 1, wherein A is amino, N-alkyl amino or a polyamine moiety.

12. The compound according to Claim 11, wherein A is amino or N-alkyl amino having from 1 to 4 carbon atoms in the alkyl group.

13. The compound according to Claim 12, wherein A is amino.

14. The compound according to Claim 11, wherein A is a polyamine moiety having from 2 to 12 amine nitrogen atoms and from 2 to 40 carbon atoms.

15. The compound according to Claim 14, wherein A is a polyamine moiety derived from a polyalkylene polyamine containing from 2 to 12 amine nitrogen polyamine atoms and from 2 to 24 carbon atoms.

16. The compound according to Claim 15, wherein the polyalkylene polyamine has the formula:
H2N-(R3-NH)Z-H
wherein R3 is an alkylene group having from 2 to 6 carbon atoms and z is an integer from about 1 to about 4.

17. The compound according to Claim 16, wherein R3 is an alkylene group having from 2 to 4 carbon atoms.

18. The compound according to Claim 17, wherein the polyalkylene polyamine is ethylene diamine or diethylene triamine.

19. The compound according to Claim 18, wherein the polyalkylene polyamine is ethylene diamine.

20. The compound according to Claim 1, wherein R is a polyalkyl group derived from polyisobutene, R1 and R2 are hydrogen and A is amino or a polyamine moiety derived from ethylene diamine.

21. A fuel composition comprising a major amount of hydrocarbons boiling in the gasoline or diesel range and an effective deposit-controlling amount of a compound of the formula:
or a fuel-soluble salt thereof, wherein R is a polyalkyl group having an average molecular weight in the range of about 600 to 5,000;
R1 and R2 are independently hydrogen or lower alkyl having 1 to 6 carbon atoms; and A is amino, N-alkyl amino having 1 to 20 carbon atoms in the alkyl group, N,N-dialkyl amino having 1 to 20 carbon atoms in each alkyl group, or a polyamine moiety having 2 to 12 amine nitrogen atoms and 2 to 40 carbon atoms.

22. The fuel composition according to Claim 21, wherein one of R1 and R2 is hydrogen or lower alkyl of 1 to 4 carbon atoms, and the other is hydrogen.

23. The fuel composition according to Claim 22, wherein one of R1 and R2 is hydrogen, methyl or ethyl, and the other is hydrogen.

24. The fuel composition according to Claim 23, wherein R2 is hydrogen, methyl or ethyl, and R1 is hydrogen.

25. The fuel composition according to Claim 21, wherein R is a polyalkyl group having an average molecular weight in the range of about 600 to 3,000.

26. The fuel composition according to Claim 25, wherein R is a polyalkyl group having an average molecular weight in the range of about 700 to 3,000.

27. The fuel composition according to Claim 26, wherein R is a polyalkyl group having an average molecular weight in the range of about 900 to 2,500.

28. The fuel composition according to Claim 21, wherein R is a polyalkyl group derived from polypropylene, polybutene, or a polyalphaolefin oligomer of 1-octene or 1-decene.

29. The fuel composition according to Claim 28, wherein R is a polyalkyl group derived from polyisobutene.

30. The fuel composition according to Claim 29, wherein the polyisobutene contains at least about 20% of a methylvinylidene isomer.

31. The fuel composition according to Claim 21, wherein A is amino, N-alkyl amino or a polyamine moiety.

32. The fuel composition according to Claim 31, wherein A is amino or N-alkyl amino having from 1 to 4 carbon atoms in the alkyl group.

33. The fuel composition according to Claim 32, wherein A is amino.

34. The fuel composition according to Claim 31, wherein A is a polyamine moiety having from 2 to 12 amine nitrogen atoms and from 2 to 40 carbon atoms.

35. The fuel composition according to Claim 34, wherein A is a polyamine moiety derived from a polyalkylene polyamine containing from 2 to 12 amine nitrogen polyamine atoms and from 2 to 24 carbon atoms.

36. The fuel composition according to Claim 35, wherein the polyalkylene polyamine has the formula:

H2N-(R3-NH)z-H

wherein R3 is an alkylene group having from 2 to 6 carbon atoms and z is an integer from about 1 to about 4.

37. The fuel composition according to Claim 36, wherein R3 is an alkylene group having from 2 to 4 carbon atoms.

38. The fuel composition according to Claim 37, wherein the polyalkylene polyamine is ethylene diamine or diethylene triamine.

39. The fuel composition according to Claim 38, wherein the polyalkylene polyamine is ethylene diamine.

40. The fuel composition according to Claim 21, wherein R is a polyalkyl group derived from polyisobutene, R1 and R2 are hydrogen and A is amino or a polyamine moiety derived from ethylene diamine.

41. The fuel composition according to Claim 21, wherein the composition contains from about 50 to about 2,000 parts per million by weight of said compound.

42. The fuel composition according to Claim 21, where the composition further contains from about 100 to about 5,000 parts per million by weight of a fuel-soluble, nonvolatile carrier fluid.

43. A fuel concentrate comprising an inert stable oleophilic organic solvent boiling in the range of from about 65°C
to 205°C and from about 10 to about 70 weight percent of a compound of the formula:
or a fuel-soluble salt thereof, wherein R is a polyalkyl group having an average molecular weight in the range of about 600 to 5,000;
R1 and R2 are independently hydrogen or lower alkyl having 1 to 6 carbon atoms; and A is amino, N-alkyl amino having 1 to 20 carbon atoms in the alkyl group, N,N-dialkyl amino having 1 to 20 carbon atoms in each alkyl group, or a polyamine moiety having 2 to 12 amine nitrogen atoms and 2 to 40 carbon atoms.

44. The fuel concentrate according to Claim 43, wherein one of R1 and R2 is hydrogen or lower alkyl of 1 to 4 carbon atoms, and the other is hydrogen.

45. The fuel concentrate according to Claim 44, wherein one of R1 and R2 is hydrogen, methyl or ethyl, and the other is hydrogen.

46. The fuel concentrate according to Claim 45, wherein R2 is hydrogen, methyl or ethyl, and R1 is hydrogen.

47. The fuel concentrate according to Claim 43, wherein R is a polyalkyl group having an average molecular weight in the range of about 600 to 3,000.

48. The fuel concentrate according to Claim 47, wherein R is a polyalkyl group having an average molecular weight in the range of about 700 to 3,000.

49. The fuel concentrate according to Claim 48, wherein R is a polyalkyl group having an average molecular weight in the range of about 900 to 2,500.

50. The fuel concentrate according to Claim 43, wherein R is a polyalkyl group derived from polypropylene, polybutene, or a polyalphaolefin oligomer of 1-octene or 1-decene.

51. The fuel concentrate according to Claim 50, wherein R is a polyalkyl group derived from polyisobutene.

52. The fuel concentrate according to Claim 51, wherein the polyisobutene contains at least about 20% of a methylvinylidene isomer.

53. The fuel concentrate according to Claim 43, wherein A is amino, N-alkyl amino or a polyamine moiety.

54. The fuel concentrate according to Claim 53; wherein A is amino or N-alkyl amino having from 1 to 4 carbon atoms in the alkyl group.

55. The fuel concentrate according to Claim 54, wherein A is amino.

56. The fuel composition according to Claim 53, wherein A
is a polyamine moiety having from 2 to 12 amine nitrogen atoms and from 2 to 40 carbon atoms.

57. The fuel concentrate according to Claim 56, wherein A is a polyamine moiety derived from a polyalkylene polyamine containing from 2 to 12 amine nitrogen polyamine atoms and from 2 to 24 carbon atoms.

58. The fuel concentrate according to Claim 57, wherein the polyalkylene polyamine has the formula:
H2N-(R3-NH)z-H
wherein R3 is an alkylene group having from 2 to 6 carbon atoms and z is an integer from about 1 to about 4.

59. The fuel concentrate according to Claim 58, wherein R3 is an alkylene group having from 2 to 4 carbon atoms.

60. The fuel concentrate according to Claim 59, wherein the polyalkylene polyamine is ethylene diamine or diethylene triamine.

61. The fuel concentrate according to Claim 60, wherein the polyalkylene polyamine is ethylene diamine.

62. The fuel concentrate according to Claim 43, wherein R is a polyalkyl group derived from polyisobutene, R1 and R2 are hydrogen and A is amino or a polyamine moiety derived from ethylene diamine.

63. The fuel concentrate according to Claim 43, wherein the fuel concentrate further contains from about 20 to about 60 weight percent of a fuel-soluble, nonvolatile carrier fluid.