MANNICH CONDENSATION PRODUCTS OF POLY(OXYALKYLENE) HYDROXYAROMATIC ETHERS AND FUEL COMPOSITIONS CONTAINING THE SAME

17-05-1996 дата публикации
Номер:
CA0002178737A1
Принадлежит: Individual
Контакты:
Номер заявки: 2178737
Дата заявки: 01-11-1995

[1]

WO 96/14371 PCT/US95/14172 01 MANNICH CONDENSATION PRODUCTS 02 OF POLY(OXYAIiKYLENE) HYDROXYAROMATIC ETHERS 03 AND FUEL COMPOSITIONS CONTAINING THE SAME 05 BACKGROUND OF THE INVENTION 07 Field of the Invention 09 This invention relates to Mannich condensation products of certain poly(oxyaIkylene) hydroxyaromatic ethers. In a 11 further aspect, this invention relates to the use of such 12 compounds in fuel compositions to prevent and control engine 13 deposits.

[2]

it is well known that automobile engines tend to form 16 deposits on the surface of engine components, such as 17 carburetor ports, throttle bodies, fuel injectors, intake 18 ports and intake valves, due to the oxidation and 19 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 27 numerous such materials are known in the art.

[3]

29 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 2Î78737 WO 96/14371 * v ' -* ' PCT/US9S/14172 01 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 3500- 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 08 gasoline engine, but also enhance the performance of the 09 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.

[4]

13 similarly, U.S. Patent No. 4,134,846, issued January 16, 14 1979 to Machleder et al., discloses a fuel additive composition comprising a mixture of (1) the reaction product 16 of an aliphatic hydrocarbon-substituted phenol, 17 epichlorohydrin and a primary or secondary mono- or 18 polyamine, and (2) a polyalkylene phenol. This patent 19 teaches that such compositions show excellent carburetor, induction system and combustion chamber detergency and, in 21 addition, provide effective rust inhibition when used in 22 hydrocarbon fuels at low concentrations.

[5]

24 Amino phenols are also known to function as detergents/dispersants, antioxidants and anti-corrosion 26 agents when used in fuel compositions. U.S. Patent 27 No. 4,320,021, issued March 16, 1982 to R. M. Lange, for 28 example, discloses amino phenols having at least one 29 substantially saturated hydrocarbon-based substituent of at least 30 carbon atoms. The amino phenols of this patent are 31 taught to impart useful and desirable properties to 32 oil-based lubricants and normally liquid fuels.

[6]

WO 96/14371 PCT/US95/14172 01 Nitro phenols have also been employed as fuel additives.

[7]

02 For example, U.S. Patent No. 4,347,148, issued August 31, 03 1982 to K. E. Davis, discloses nitro phenols containing at 04 least one aliphatic substituent,having at least about 05 40 carbon atoms. The nitro phenols of this patent are 06 taught to be useful as detergents, dispersants, antioxidants 07 and demulsifiers for lubricating oil and fuel compositions.

[8]

09 in addition, U.S. Patent No. 4,231,759, issued November 4, 1980 to Udelhofen et al., discloses a fuel additive 11 composition comprising the Mannich condensation product of 12 (i) a high molecular weight alkyl-substituted 13 hydroxyaromatic compound wherein the alkyl group has a 14 number average molecular weight of about 600 to about 3000, (2) an amine, and (3) an aldehyde. This patent teaches that 16 such Mannich condensation products provide carburetor 17 cleanliness when employed alone, and intake valve 18 cleanliness when employed in combination with a hydrocarbon 19 carrier fluid.

[9]

21 U.S. Patent No. 4,859,210, issued August 22, 1989 to Franz 22 et al., discloses fuel compositions containing (1) one or 23 more polybutyl or polyisobutyl alcohols wherein the 24 polybutyl or polyisobutyl group has a number average molecular weight of 324 to 3000, or (2) a poly(alkoxylate) 26 of the polybutyl or polyisobutyl alcohol, or (3) a 27 carboxylate ester of the polybutyl or polyisobutyl alcohol.

[10]

28 This patent further teaches that when the fuel composition 29 contains an ester of a polybutyl or polyisobutyl alcohol, the ester-forming acid group may be derived from saturated 31 or unsaturated, aliphatic or aromatic, acyclic or cyclic 32 mono- or polycarboxylic acids.

[11]

WO 96/14371 .> , y q y PCT/US95/14172 01 U.S. Patent No. 3,285,855, issued November 15, 1966 to 02 Dexter et al., discloses alkyl esters of dialkyl 03 hydroxybenzoic and hydroxyphenylalkanoic acids wherein the 04 ester moiety contains from 6 to 30 carbon atoms. This 05 patent teaches that such esters are useful for stabilizing 06 polypropylene and other organic material normally subject to 07 oxidative deterioration, similar alkyl esters containing 08 hindered dialkyl hydroxyphenyl groups are disclosed in U.S.

[12]

09 Patent No. 5,196,565, which issued March 23, 1993 to Ross.

[13]

11 U.S. Patent No. 5,196,142, issued March 23, 1993 to Mollet 12 et al., discloses alkyl esters of hydroxyphenyl carboxylic 13 acids wherein the ester moiety may contain up to 23 carbon 14 atoms. This patent teaches that such compounds are useful as antioxidants for stabilizing emulsion-polymerized 16 polymers.

[14]

18 Fuel additives containing a poly(oxyalkylene) moiety are 19 also known in the art. For example, U.S. Patent No. 4,191,537, issued March 4, 1980 to R. A. Lewis et al., 21 discloses a fuel composition comprising a major portion of 22 hydrocarbons boiling in the gasoline range and from 30 to 23 2000 ppm of a hydrocarbyl poly(oxyalkylene) aminocarbamate 24 having a molecular weight from about 600 to 10,000, and at least one basic nitrogen atom. The hydrocarbyl 26 poly(oxyalkylene) moiety is composed of oxyalkylene units 27 selected from 2 to 5 carbon oxyalkylene units. These fuel 28 compositions are taught to maintain the cleanliness of 29 intake systems without contributing to combustion chamber deposits.

[15]

32 Aromatic compounds containing a poly(oxyalkylene) moiety are 33 also known in the art. For example, the above-mentioned 34 U.S. Patent No. 4,191,537, discloses alkylphenyl 2Î78737 WO 96/14371 PCT/US95/14172 01 poly(oxyalkylene) polymers which are useful as intermediates 02 in the preparation of alkylphenyl poly(oxyalkylene) 03 aminocarfaamates.

[16]

05 Additionally, hydroxyaromatic compounds containing a 06 poly(oxyalkylene) moiety are known in the art. For example, 07 U.S. Patent No. 4 y52,732, issued August 28, 1990 to G. P.

[17]

08 Speranza et al., discloses Mannich condensates prepared from 09 a phenol, formaldehyde and an alkylamine containing propoxy groups and, optionally, ethoxy groups. These Mannich 11 condensates are taught to be useful as corrosion inhibitors, 12 water repellant agents, paint adhesion promoters, and also 13 as intermediates for preparing surfactants, and pololys 1* finding use in the manufacture of polyurethane foam.

[18]

16 My prior commonly assigned copending U.S. Patent Application 18 certain poly(oxyalkylene) hydroxyaromatic ethers which 19 provide excellent control of engine deposits, especially intake valve deposits, when employed as fuel additives in 21 fuel compositions. These poly(oxyalkylene) hydroxyaromatic 22 ethers have been found to produce fewer combustion chamber 23 deposits than known aliphatic hydrocarbon-substituted 24 phenolic fuel additives.

[19]

2* SUMMARY OF THE INVENTION 28 it has now been discovered that certain Mannich condensation 29 products of poly(oxyalkylene) hydroxyaromatic ethers also provide excellent control of engine deposit, including intake valve deposits, with fewer combustion chamber deposit ii when employed as fuel additives, and further provide 33 excellent control of injector deposits.

[20]

2178737 * % R- WO 96/14371 f PCT/US95/14172 01 More specifically, the compounds of the present invention 02 are Mannich condensation products prepared by the reaction 03 of a poly(oxyalkylene) hydroxyaromatic ether of the formula:

[21]

07 Rj-fc j-(CH2)]r-{0-CIt-CH)irO5 12 R3 and R4 are each independently hydrogen or lower alkyl 13 having 1 to 6 carbon atoms; R5 is hydrogen, alkyl having 1 to 30 carbon atoms, phenyl, 16 aralkyl or alkaryl having 7 to 3 6 carbon atoms, or an acyl 17 group having the formula:

[22]

19 II Ï or j| __<>_ _o_(CH2}u-C02R7 wherein Rjl is hydrogen, hydroxy, lower alkyl having 1 to 6 carbon atoms, or lower alkoxy having 1 to 6 carbon atoms; wherein R is alkyl having 1 to 30 carbon atoms, phenyl, or aralkyl or alkaryl having 7 to 36 carbon atoms; R7 is alkyl having 1 to about 10 carbon atoms; and u is an integer from 1 to 10; n is an integer from 5 to 100; and x is an integer from 0 to 10; with-an aldehyde having the formula inCCO), wherein R2 is hydrogen or lower alkyl having 1 to 6 carbon atoms, and a nitrogen base selected from ammonia, lower alkylamine having 1 to 6 carbon atoms, a polyamine having 2 to about 12 amine « 2178737 WO 96/14371 PCT/US95/14172 01 nitrogen atoms and 2 to about 40 carbon atoms and mixtures 02 thereof.

[23]

04 Fuel soluble salts of the present Mannich condensation 05 products are also contemplated and can be prepared by 06 conventional procedures, for example, by reaction with an 07 appropriate acid or base.

[24]

09 As is frequently the case with Mannich condensation products, the reaction product is typically a mixture of 11 products because of competing or sequential reactions which 12 result in secondary or derivative products, such as 13 cross-linked products.

[25]

The amine moiety of the Mannich condensation product is 16 preferably derived from a polyamine having from 2 to about 17 12 amine nitrogen atoms and from 2 to about 40 carbon atoms.

[26]

18 The polyamine preferably has a carbon-to-nitrogen ratio of 19 from about 1:1 to about 10:1. The polyamine may be substituted with substituents selected from hydrogen, 21 hydrocarbyl groups of from 1 to about 10 carbon atoms, acyl 22 groups of from 2 to about 10 carbon atoms, and monoketone, 23 monohydroxy, mononitro, monocyano, alkyl and alkoxy 24 derivatives of hydrocarbyl groups of from 1 to 10 carbon atoms. It is preferable that at least one of the basic 26 nitrogen atoms of the polyamine is a primary or secondary 27 amino nitrogen. The polyamine component employed in the 28 present invention has been described and exemplified more 29 fully in U.S. Patent No. 4,191,537, the disclosure of which is incorporated by reference herein.

[27]

32 The base product and, in general, the principal Mannich 33 condensation product of the invention can be represented by 34 the formula:

[28]

2178737 • WO 96/14371 PCT/US95/14172 01 % 02 9? I OZ i CH-Y 03 R \ch2) x-(o-cit-<:H) ,,-0% (I) R3 ' R4 R3 and R4 are each independently hydrogen or lower alkyl having 1 to 6 carbon atoms; R5 is hydrogen, alkyl having 1 to 3 0 carbon atoms, phenyl, aralkyl or alkaryl having 7 to 36 carbon atoms, or an acyl group having the formula:

[29]

08 wherein is hydrogen, hydroxy, lower alkyl having 1 to 09 6 carbon atoms, or lower alkoxy having 1 to 6 carbon atoms; X0 11 Rj is hydrogen or lower alkyl having 1 to 6 carbon atoms; - « ? 21 I or I 22 -<!-«« -O-(CH2)u-C02R7 24 wherein R is alkyl having 1 to 30 carbon atoms, phenyl, or aralkyl or alkaryl having 7 to 36 carbon atoms; R7is alkyl 26 having 1 to about 10 carbon atoms; and u is an integer from 27 1 to 10; 29 n is an integer from 5 to 100; and x is an integer from 0 to 10; 32 Y is selected from amino, lower alkylamino having 1 through 33 6 carbon atoms or a polyamine radical, preferably a 34 polyalkylene polyamine, having 2 through 12 amine nitrogen WO96/14371 >- * t Ut Jt PCr/US95/14172 01 atoms and 2 through 40 carbon atoms, wherein the attachment 02 of Y to the methylene linking group, i.e., —CH)—, is 03 through one of its amine nitrogen atoms. It is also 0* understood that the -CH%-Y substituent is ortho to a 05 hydroxy group on the aromatic ring and the remaining 06 substituents may be at any available position on the 07 aromatic ring.

[30]

09 In general, the commercial product will be a mixture of compounds according to formula I because, as noted above, 11 the reaction product will be a mixture of products. In *2 general, there is no commercial reason to isolate individual 13 compounds. If desired, the individual compounds of 14 formula I could be prepared by using individual compounds as starting materials and by isolating individual compounds 16 from the product. But, as noted above, there is normally no 17 commercial reason to isolate particular compounds when the 18 product is used as a fuel additive and it generally would 19 not be economical.

[31]

21 The present invention further provides a fuel composition 22 comprising a major amount of hydrocarbons boiling in the 23 gasoline or diesel range and an effective 2* deposit-controlling amount of a compound or mixture of compounds of the present invention.

[32]

27 The present invention additionally provides a fuel 28 concentrate comprising an inert stable oleophilic organic 29 solvent boiling in the range of from about 150oF to 400oF and from about 10 to 70 weight percent of a compound or 31 mixture of compounds of the present invention.

[33]

WO 96/14371 PCT/US95/14Î72 01 Among other factors, the present invention is based on the 02 discovery that certain Mannich condensation products of 03 poly(oxyalkylene) hydroxyaromatic ethers are surprisingly 04 useful for reducing engine deposits, especially on intake 05 valves, when employed as fuel additives in fuel 0 6 compos it ions.

[34]

08 DETAILED DESCRIPTION OF THE INVENTION As noted above, because of competing or secondary reactions 11 the Mannich condensation product of the present invention is 12 typically a mixture of compounds. For example, where a long 13 chain polyalkylene polyamine reactant is used, although the 14 principal attachment of the polyamine radical to the benzyl ring will occur at the terminal nitrogen atoms, attachment 16 can also occur at an internal amino nitrogen atom. Further, 17 because of competing secondary reactions, cross-linked 18 products are also produced. Thus, for example, in the case 19 where diethylene triamine is the amine reactant, a significant amount of the bis product will also be produced, 21 that is,:

[35]

23 OH Rj 1*2 9H -CHNHCH2CH2NHCH2CH2NHCH-| 27 (CH2)x-(OCHCH)n-OR5 RjO-fCHCHOJ-fCHj) È3R4 4% wherein R R R3, R4, 1 x and n are as <lefined above.

[36]

The polyamine reactant used in the present invention is preferably an acyclic polyamine having terminal amino WO 96/14371 2178737 PCT/US95/14I72 OS nitrogen atoms or less preferably a nitrogen heterocycle.

[37]

In each case the amino nitrogen atoms are separated from each other by at least two carbon atoms. As noted above, the polyamine preferably has a carbon-to-nitrogen ratio of from about 1:1 to about 10:1. The polyamine may be substituted with substituents selected from hydrogen, hydrocarbyl groups of from l to about 10 carbon atoms, acyl grounds of from 2 to about 10 carbon atoms, and monoketone, monohydroxy, mononitro, monocyano, alkyl and alkoxy derivatives of hydrocarbyl groups of about from 1 to carbon atoms. It is preferable that at least one of the basic nitrogen atoms of the polyamine is a primary or secondary amino nitrogen. The polyamine component employed in the present invention has been described and exemplified more fully in U.S. Patent No. 4,191,537.

[38]

Hydrocarbyl, as used above, denotes an organic radical composed of carbon and hydrogen which may be aliphatic, alicyclic, aromatic or combinations thereof, e.g., aralkyl.

[39]

Preferably, the hydrocarbyl group will be relatively free of aliphatic unsaturation, i.e., ethylenic and acetylenic, particularly acetylenic unsaturation. The substituted polyalkylene amines used in the present invention are generally, but not necessarily, N-substituted polyamines.

[40]

Exemplary hydrocarbyl groups and substituted hydrocarbyl groups include alkyIs such as methyl, ethyl, propyl, butyl, isobutyl, pentyl, hexyl, octyl, etc., alkenyls such as propenyl, isobutenyl, hexenyl, octenyl, etc., hydroxyalkyls, such as 2-hydroxyethyl, 3-hydroxypropyl, hydroxy-isopropyl, 4-hydroxybutyl, etc., ketoalkyls, such as 2-ketopropyl, 6-ketooctyl, etc., alkoxy and lower alkenoxy alkyls, such as ethoxyethyl, ethoxypropy1, propoxyethy1, propoxypropyl, diethyleneoxymethyl, triethyleneoxyethyl, tetraethyleneoxyethyl, diethyleneoxyhexyl, etc. The 217873? WO 96/14371 PCT/US95/14172 01 aforementioned acyl groups are such as propionyl, acetyl, 02 etc. The more preferred substituents are hydrogen, C-Cg 03 alky Is and C hydroxyalkyls.

[41]

05 In the substituted polyalkylene amine, the substituents are 06 found at any atom capable of receiving them. The 07 substituted atoms, e.g., substituted nitrogen atoms, are 08 generally geometrically inequivalent, and consequently the 09 substituted amines finding use in the present invention can be mixtures of mono- and poly-substituted polyamines with 11 substituent groups situated at equivalent and/or 12 inequivalent atoms.

[42]

14 Although, as noted above, a wide range of substituted and unsubstituted polyamines can be used, resulting in the 16 corresponding Mannich condensation product, in general 17 polyalkylene polyamines, including alkylene diamine, and 18 including substituted polyalkyleneamines, e.g., alkyl and 19 hydroxyalkyl-substituted polyalkylene polyamine are preferred. Preferably, the alkyl group linking the amino 21 nitrogen groups contains from 2 to 6 carbon atoms, there 22 being preferably from 2 to 3 carbon atoms between the 23 nitrogen atoms. Such groups are exemplified by ethylene, 2* 1,2-propylene, 2,2-dimethyl-propylene, trimethylene, 1,3,2-hydroxypropylene, etc. Examples of the polyalkylene 26 amines from which such radicals are derived include ethylene 27 diamine, diethylene triamine, di(trimethylene) triamine, 28 dipropylene triamine, triethylene tetraamine, tripropylene 29 tetraamine, tetraethylene pentamine, and pentaethylene hexamine. Such amines encompass isomers such as 31 branched-chain polyamines and previously mentioned 32 substituted polyamines, including hydroxy- and 33 hydrocarbyl-substituted polyamines. Among the polyalkylene WO96/14371 Uf J/ PCT/US95/14172 01 polyamines, those containing 2-12 amino nitrogen atoms and 02 2-24 carbon atoms are especially preferred, and tlie C-C 03 alkylene polyamines are most preferred, that is, ethylene 04 diamine, polyethylene polyamine, propylene diamine and 05 polypropylene polyamine, and in particular, the lower 0« polyalkylene polyamines, e.g., ethylene diamine, dipropylene 07 triamine, etc. A particularly preferred polyalkylene 08 polyamiaa is diethylene triamine.

[43]

«rhe amine component of the present fuel additive also may be 11 derived from heterocyclic polyamines, heterocyclic 12 substituted amines and substituted heterocyclic compounds, 13 wherein the heterocycle comprises one or more 5-6 membered 14 rings containing oxygen and/or nitrogen. Such heterocyclic rings may be saturated or unsaturated and substituted with groups selected from the aforementioned substituents. The heterocyclic compounds are exemplified by piperazines, such 18 as 2-methylpiperazine, N-(2-hydroxyethyl)piperazine, 19 lf2-bis-(N-pijpj@razinyl)ethane and M'-bisfN-piperazinylJpiperazine, 2-methyl-imidazoline, 21 3-amino-piperidine, 3-aminopyridine, N-(3.-aminopropyi)- 22 morpholine, etc. Among the heterocyclic compounds, the 23 piperazines are preferred.

[44]

in terms of deposit control performance and/or manufacturing 26 ease or blending facility, the preferred Mannich 27 condensation products are, referring to the substituents 28 identified in formula I and the corresponding fuel-soluble 29 salts thereof, those, having at least one of the following preferred substituents and more preferably two or more.

[45]

WO 96/14371 PCT/US95/14172 01 Preferably, is hydrogen, hydroxy, or lower alkyl having 1 02 to 4 carbon atoms. More preferably, % is hydrogen or 03 hydroxy. Most preferably, Ri is hydrogen.

[46]

05 Preferably, Y is a radical derived from an unsubstituted 06 polyalkylene polyamine, more preferably polyethylene 07 polyamines or polypropylene polyamines, including ethylene 08 diamine and propylene diamine.

[47]

Rj is preferably hydrogen or lower alkyl having 1 to 11 4 carbon atoms. More preferably, Rj is hydrogen.

[48]

Preferably, one of J and R4 is lower alkyl having 1 to 3 carbon atoms and the other is hydrogen. More preferably, one of % and R4 is methyl or ethyl and the other is hydrogen. Most preferably, one of R3 and R4 is ethyl and the other is hydrogen.

[49]

Rj is preferably hydrogen, alkyl having 1 to 24 carbon atoms, or alkylphenyl or phenylalkyl having an alkyl group containing 1 to 24 carbon atoms. More preferably, R5 is hydrogen, alkyl having 4 to 12 carbon atoms or alkylphenyl or phenylalkyl having an alkyl group containing 1 to 12 carbon atoms. Most preferably, R5 is hydrogen or alkylphenyl or phenylalkyl having an alkyl group containing 1 to 12 carbon atoms.

[50]

Rg is preferably alkyl having 4 to 12 carbon atoms.

[51]

Preferably, h is an integer from 10 to 50. More preferably, n is an integer from 15 to 30. Preferably, x is an integer from 0 to 2. More preferably, x is 0.

[52]

WO 96/14371 Vij[ PCT/US95/14172 01 A preferred group of Mannich condensation products are those 02 of formula I wherein Rj is hydrogen, hydroxy, or lower alkyl having 1 to 4 carbon atoms; % is hydrogen; one of R3 and "R is hydrogen and the other is methyl or ethyl; Rj is hydrogen, alkyl having 1 to about 24 carbon atoms or alkylphenyl or phenylalkyl having an alkyl group containing 1 to about 24 carbon atoms; n is 15 to 30 and x is 0; and Y is a polyethylene polyamine radical, including ethylene 09 diamine.

[53]

Another preferred group of Mannich condensation products are those of formula I wherein Rj is hydrogen, hydroxy, or lower alkyl having 1 to 4 carbon atoms; R2 is hydrogen; one of R3 and R4 is hydrogen and the other is methyl or ethyl; R5 is hydrogen, alkyl having l to about 24 carbon atoms or alkylphenyl or phenylalkyl having an alkyl group containing 1 to about 24 carbon atoms; n is 15 to 30; x is 1 or 2; and Y is a polyethylene polyamine radical, including ethylene diamine.

[54]

A more preferred group of Mannich condensation products are those of formula I wherein Rj is hydrogen or hydroxy; R2 is hydrogen; one of R3 and R is hydrogen and the other is methyl or ethyl; T is hydrogen, alkyl having 4 to 12 carbon atoms or alkylphenyl or phenylalkyl having an alkyl group containing 1 to 12 carbon atoms; n is 15 to 30; x is 0; and Y is an ethylene diamine or diethylene triamine radical.

[55]

It is especially preferred that the aromatic hydroxyl group or groups present in the compounds of formula I, above, be situated in a meta or para position relative to the poly(oxyalkylene) ether moiety.

[56]

WO 96/14371 il fbl JJ PCT/US95/14172 01 Generally, the poly(oxyalkylene) hydroxyaromatic ethers of 02 this invention will contain an average of about 5 to about 03 100 oxyalkylene units; preferably, 10 to 50 oxyalkylene 04 units; more preferably, 15 to 30 oxyalkylene units.

[57]

06 Preferably, the compounds of the present invention will have 07 a sufficient molecular weight so as to be non-volatile at 08 normal engine intake valve operating temperatures (about 09 200-250oC). Typically, the average molecular weight of the primary or monomeric reaction product, i.e., the compounds 11 of formula I, will range from about 550 to about 6000. More 12 preferably, the compound and salts have an average molecular 13 weight of about from 600 to 4000, more preferably from 700 14 to 3000. Generally average molecular weight will primarily be a function of the poly(oxyalkylene) ether substituent but 16 can also be influenced by the chain length of the polyamine 17 substituent. The molecular weight of the product mixture 18 will also be affected by cross-linking. Thus, the primary 19 considerations are volatility and fuel solubility and not the technical molecular weight of the product mixture.

[58]

22 Fuel soluble salts of the Mannich condensation products are 23 also useful for preventing or controlling engine deposits 24 and, in some cases, may improve solubility. Suitable salts include, for example, those obtained by protonating the 26 amino moiety with an acid or deprotonating the phenol moiety 27 with a base. Preferred salts are derived from 28 toluenesulfonic acid and methanesulfonic acid or are alkali 29 metal and substituted ammonium salts.

[59]

31 Definitions 33 As used herein, the following terms have the following 34 meanings unless expressly stated to the contrary.

[60]

WO 96/14371 PCT7US9S/14172 01 The term "alkyl" refers to both straight- and branched-chain 02 alkyl groups.

[61]

04 The term "lower alkyl" refers to alkyl groups having 1 to 05 about 6 carbon atoms and includes primary, secondary and 06 tertiary alkyl groups. Typical lower alkyl groups include, 07 for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, 08 sec-butyl, t-butyl, n-pentyl, n-hexyl and the like.

[62]

The term "lower alkoxy" refers to the group -OR wherein R, 11 is lower alkyl. Typical lower alkoxy groups include 12 methoxy, ethoxy, and the like.

[63]

14 The term "alkaryl" refers to the group:

[64]

wherein R and R are each independently hydrogen or an alkyl group, with the proviso that both.Rfc and Rc are not hydrogen. Typical alkaryl groups include, for example, tolyl, xylyl, cumenyl, ethylphenyl, butylphenyl, dibutylphenyl, hexylphenyl, octylphenyl, dioctylphenyl, nonylphenyl, decylphenyl, didecyIpheny1, dodecylphenyl, hexadecylphenyl, octadecylphenyl, icosylphenyl, tricontyIpheny1 and the like. The term "aIkyIpheny1" refers to an alkaryl group of the above formula in which Rj, is alkyl and Rc is hydrogen.

[65]

9 1 7 Q 7 X7 4fe WO 96/14371 PCT/US95/14172 01 The term "aralkyl" refers to the group:

[66]

05 R*"--/ 07 wherein Rj and î are each independently hydrogen or an 08 alkyl group; and Rf is an alkylene group. Typical aralkyl groups include, for example, benzyl, methylbenzyl, dimethylbenzyl, phenethyl, and the like.

[67]

The term "oxyalkylene unit" refers to an ether moiety having the general formula:

[68]

Rg Rh I I —O-CH-CB- 19 wherein R and T are each independently hydrogen or lower alkyl groups.

[69]

22 The term "poly(oxyalkylene)" refers to a polymer or oligomer 23 having the general formula:

[70]

g % 26 _(0_CH_CH)z_ 28 wherein Rg and Rh are as defined above, and z is an integer 29 greater than 1. When referring herein to the number of poly(oxyalkylene) units in a particular poly(oxyalkylene) 31 compound, it is to be understood that this number refers to 32 the average number of poly(oxyalkylene) units in such 33 compounds unless expressly stated to the contrary.

[71]

2\nm WO 96/14371 PCmrS95/14172 01 The term "polyamine" as used herein refers to polyamines 02 containing 2 to 12 amine nitrogen atoms and 2 to 40 carbon 03 atoms and includes both acyclic and cyclic polyamines and 04 may be substituted with a variety of substituents so long as 05 the substitution does not significantly adversely affect the 06 deposit control and fuel compatibility properties of the 07 present compositions.

[72]

09 The term "polyalkylene polyamine" by definition contains at least two amine groups.

[73]

12 The term "fuel" refers to liquid hydrocarbon compounds such 1* as petroleum fuels or synthetic fuels which are useful as l* fuels in spark ignition or combustion fire engines and may also contain minor amounts of other auxiliary fuels.

[74]

17 The tenu "engine" refers to internal combustion engines and 18 includes both spark ignition engines and combustion fired 19 engines such as diesel engines.

[75]

21 SYNTHESIS 23 The compounds of formula I can be conveniently prepared by 24 the following schematically represented process:

[76]

26 OH 0 OH Rj + H-Y + HRjC - |-Y~CH_Y + H20 (B) (C) IV (CH2)X— <OCHCH)n—OR5 {CH2JX—(OCHCHJnORj 31 II M 32 R3 R4 % R4 33 (A) (I) WO 96/14371 PCT7US95/14172 01 wherein R1, Rj, %, R4, %/ Y, n and x are as defined 02 hereinabove.

[77]

04 This process can be conducted by contacting reactants (A), 05 (B) and (C) under reactive conditions, optionally in an 06 inert solvent or liquid reaction medium. Typically, the 07 reaction is conducted at temperatures in the range of about from 250C to 2000C/ preferably 750C to 150oC for about from 1 to 50 hours, preferably 5 to 20 hours using mole ratios of reactant in the range of about from 0.1 to 10, preferably 11 0.3 to 3 moles of reactant (B) and 0.1 to 10, preferably l 12 to 5 moles of aldehyde (C) per mole of A. Suitable inert 13 organic solvents or liquid diluents (reaction medium) which H can be used include, for example, toluene, xylene, chloroform, acetonitrile, and the like, and compatible 16 mixtures thereof. Again, although the reaction product is 17 shown for convenience as formula (1) the condensation 18 product will generally be a mixture of products reflecting 19 competing and secondary reaction products; such as, for example, further reactions or cross-linking of amino 21 nitrogens in the polyalkylene amine substituent.

[78]

23 Reactant (B) is the compound form corresponding to the 2* radical Y and includes ammonia, lower alkyl amine (for example, methylamine, isopropylamine, dipropylamine or 26 hexylamine) and polyamines as defined hereinabove. The 27 polyamine must contain at least one primary or secondary 28 amino group because the reaction proceeds by displacement of 29 one of the amino hydrogen groups. Suitable substituted and unsubstituted polyalkylene amines which can be used in the 31 aforedescribed process include, for example, ethylene 32 diamine, 1,2-propylene diamine, 1,3-propylene diamine, 33 diethylene triamine, triethylene tetraamine, hexamethylene 34 diamine, tetraethylene pentamine, dimethylaminopropylene WO 96/14371 «- l I U / J i PCT/US95/14172 01 diamine, N-Cbeta-aminoethylJpiperazine, N-(beta-aminoethyl) 02 morpholine, NN'-di(beta-aminoethyl)piperazine, 03 N'-di (beta-aminoethyl) imidazolidone, N-(beta-cyanoethyl) 04 ethane-1,2-diamine, l-amino-3,6,9-triazaoctadecane, 05 l-amino-3,6-diaza-9-oxaàecane, N-(beta-aminoethyl) 06 diethanolamine, N'-acetylmethyl-N-(beta-aminoethyl) 07 ethane-1,2-diamine, N-acetonyl-l,2-propanediamine, 08 N-(beta-nitroethyl)-l,3-propane diamine, 09 1,3-dimethyl-5-(beta-aminoethyl)hexahydrotriazine, N-(beta-aminoethyl)hexahydrotriazine, 5-(beta-aminoethyl)- 11 1,3,5-dioxazine, 2-(2-aminoethylamino)ethanol, and 12 2-[2-(2-aminoethylamino) ethylaminojethanol, and the like.

[79]

13 Again, because the commercially produced polyalkylene amines 14 are in many instances mixtures of polyalkylene amine, it is convenient to use the commercial mixture and correspondingly 16 the product of formula I will also be a mixture.

[80]

18 The commercial polyalkylamines are typically mixtures in 19 which one or several compounds predominate with the average composition indicated. For example, tetraethylene pentamine 21 prepared by the polymerization of aziridine or the reaction 22 of dichoroethylene and ammonia will have both lower and 23 higher amine members, e.g., triethylene tetraamine, 24 substituted piperazines and pentaethylene hexamine, but the composition will be mainly tetraethylene pentamine and the 26 empirical formula of the total amine composition will 27 closely approximate that of tetraethylene pentamine.

[81]

28 Finally, in preparing the compounds of this invention, where 29 the various nitrogen atoms of the polyamine are not geometrically equivalent, several substitutional isomers are 31 possible and are encompassed within the final product.

[82]

33 The above-described amines are generally known compounds 34 and, as noted above, are, in many cases, commercial WO 96/14371 Cl / 8 7 3 7 PCT/US95/14172 01 commodities and in any case can be prepared by known 02 procedures or obvious modifications thereof, e.g., 03 substitution of appropriate starting materials and 04 optimization of reaction conditions.

[83]

06 Methods of preparation of amines and their reactions are 07 detailed in Sidgewick's «The Organic Chemistry of Nitrogen", 08 Clarendon Press, Oxford, 1966; Noller's "Chemistry of 09 Organic Compounds", Saunders, Philadelphia, 2nd Ed., 1957; and Kirk-othmer's "Encyclopedia of Chemical Technology", 2nd 11 Ed., especially Volume 2, pp. 99-116.

[84]

13 The compounds of formula A, above, may be prepared by the 14 procedures described in my commonly assigned copending U.S.

[85]

16 1992, the disclosure of which is hereby incorporated by 17 reference herein in its entirety.

[86]

19 In accordance with the procedures described in U.S. Serial 21 of formula A may be prepared by the following general 22 methods and procedures. It should be appreciated that where 23 typical or preferred process conditions (e.g. reaction 24 temperatures, times, .mole ratios of reactants, solvents, pressures, etc.) are given, other process conditions may 26 also be used unless otherwise stated. Optimum reaction 27 conditions may vary with the particular reactants or 28 solvents used, but such conditions can be determined by one 29 skilled in the art by routine optimization procedures.

[87]

31 The poly(oxyalkylene) hydroxyaromatic ethers of formula A 32 may be prepared from a hydroxyaromatic compound having the 33 formula:

[88]

WO 96/14371 PCT/US95/14I72 (CH-OH (HI) 0S wherein Rj and x are as defined above.

[89]

The hydroxyaromatic compounds of formula III are either known compounds or can be prepared from known compounds by conventional procedures. Suitable hydroxyaromatic compounds for use as starting materials in this invention include catechol, resorcinol, hydroquinone, 1,2,3-trihydroxybenzene (pyrogallol), 1,2,4-trihydroxybenzene (hydroguinol), 1,3,5-trihydroxybenzene (phloroglucinol), l,4-dihydroxy-2- methylbenzene, l,3-dihydroxy-5-methylbenzene, 2-t-butyl-l,4- dihydroxybenzene, 2,6-di-t-butyl-l,4-dihydroxybenzene, 1,4-dihydroxy-2-methoxybenzene, 1,3-dihydroxy-5- methoxybenzene, 4-hydroxybenzyl alcohol, 4-hydroxyphenethyl 18 alcohol, and the like.

[90]

In a preferred method of synthesizing the poly(oxyalkylene) hydroxyaromatic ethers employed in the present invention, a hydroxyaromatic compound of formula III is first selectively protected to provide a compound having the formula:

[91]

OR10 11_u!_j_(CH2) .h (IVj wherein R10 is a suitable hydroxy1 protecting group, such as benzyl, tert-butyldimethylsilyl, methoxymethyl, and the like; Rn is hydrogen, lower alkyl, lower alkoxy, or the group -0R13, wherein R13 is a suitable hydroxy 1 protecting group, such as benzyl, tert-butyldimethylsilyl.

[92]

217873? WO 96/14371 L.liV{Jf PCTrtJS95/14172 01 methoxymethyl, and the like. Preferably, R10 and 3 are 02 benzyl; except in the case where x is 1, then Rxo and R are 03 preferably a tert-butyl-dimethylsilyl group.

[93]

os Selective protection of III may be accomplished using 06 conventional procedures. The choice of a suitable 07 protecting group for a particular hydroxyaromatic compound 08 will be apparent to those skilled in the art. Various 09 protecting groups, and their introduction and removal, are described, for example, in T. W. Greene and P. G. M. Wuts, 1?L Protective Groups In Organic Synthesis, Second Edition, 12 Wiley, New York, 1991, and references cited therein.

[94]

13 Alternatively, the protected derivatives IV can be prepared 14 from known starting materials other than the hydroxyaromatic compounds of formula III by conventional procedures. In 16 some cases, the protected derivatives IV are commercially 17 available, e.g., 4-benzyloxyphenol is conanercially available 18 from Aldrich Chemical Co., Milwaukee, Wisconsin 53233.

[95]

The protected hydroxyaromatic compound of formula IV is then 21 deprotonated with a suitable base to provide a metal salt 22 having the formula:

[96]

26 --(CH-OM (V) 28 wherein R10, Rn and x are as defined above; and M is a metal 29 cation, such as lithium, sodium or potassium.

[97]

ai Generally, this deprotonation reaction will be effected by 32 contacting IV with a strong base, such as sodium hydride, 33 potassium hydride, sodium amide and the like, in an inert WO96/14371 I I 7873? PCT/US95/14172 01 solvent, such as toluene, xylene and the like, under 02 substantially anhydrous conditions at a temperature in the 03 range from about -100C to about 120oC for about 0.25 to 04 about 3 hours.

[98]

06 Metal sa.-- V is generally not isolated, but is reacted 07 in situ with about 5 to about 100 molar equivalents of an 08 alkylene oxide (an epoxide) having the formula:

[99]

Q 11 %-HC-CH-R4 (VI) 13 wherein R3 and 1*4 are as defined above, to provide, after 14 neutralization, a poly(oxyalkylene) polymer or oligomer having the tormula:

[100]

18 A. R3 R4 (CH2)x-(O-CI-CH)n-0H (VII) wherein R3, 1*4, R10, R11, n and x are as defined above.

[101]

Typically, this polymerization reaction is conducted in a substantially anhydrous inert solvent at a temperature of about 30oC to about 150"C for about 2 to about 120 hours.

[102]

Suitable solvents for this reaction, include toluene, xylene and the like. The reaction will generally be conducted at a pressure sufficient to contain the reactants and the solvent, preferably at atmospheric or ambient pressure.

[103]

More detailed reaction conditions for preparing poly(oxyaIkylene) compounds may be found in U.S. Patent Nos. 2,782,24 0 and 2,841,479, which are incorporated herein by reference.

[104]

WO 96114371 Ci 7 87 57 PCT/US95/14172 01 The amount of alkylene oxide employed in this reaction will 02 depend on the number of oxyalkylene units desired in the 03 product. Typically, the molar ratio of alkylene oxide VI to 04 metal salt V will range from about 5:1 to about 100:1; 05 preferably, from 10:1 to 50:1, more preferably from 15:1 to 06 30:1.

[105]

08 suitable alkylene oxides for use in the polymerization 09 reaction include, for example, ethylene oxide; propylene oxide; butylène oxides, such as 1,2-butylene oxide 11 (1,2-epoxybutane) and 2,3-butylène oxide (2,3-epoxybutane); 12 pentylene oxides; hexylene oxides; octylene oxides; and the 13 like. Preferred alkylene oxides are propylene oxide and 14 1,2-butylene oxide.

[106]

16 In the polymerization reaction, a single type of alkylene 17 oxide may be employed, e.g., propylene oxide, in which case 18 the product is a homopolymer, e.g., a poly(oxypropylene).

[107]

19 However, copolymers are equally satisfactory and random copolymers are readily prepared by contacting the metal 21 salt V with a mixture of alkylene oxides, such as a mixture 22 of propylene oxide and 1,2-butylene oxide, under 23 polymerization conditions. Copolymers containing blocks of 24 oxyalkylene units are also suitable for use in the present invention. Block copolymers may be prepared by contacting 26 the metal salt V with first one alkylene oxide, then others 27 in any order, or repetitively, under polymerization 28 conditions.

[108]

Poly(oxyalkylene) polymers of formula VII may also be 31 prepared by living or immortal polymerization as described 32 by S. Inoue and T. Aida in Encyclopedia of Polymer Science 33 and Engineering, Second Edition, Supplemental Volume, 34 J. Wiley and Sons, New York, pages 412-420 (1989). These 217873? WO 96/14371 v t jf PCT/US95/14172 01 procedures are especially useful for preparing 02 poly(oxyalkylene) alcohols of formula V in which R, and 1 03 are both alkyl groups.

[109]

05 Deprotection of the aromatic hydroxyl group(s) of VII using 06 conventional procedures provides poly(oxyalkylene) 07 hydroxyaromatic ethers for use in the present invention 08 having the formula:

[110]

OH 11 Ji % R4 32 J R3 R, 33 ~ Rl"lt7l~<CH2>x-(0--C-CH)n-OH (VIII) wherein Rlf Rj, R4, n and x are as defined above.

[111]

Appropriate conditions for this deprotection step will depend upon the protecting group(s) utilized in the synthesis and wii: be readily apparent to those skilled in the art. For example, benzyl protecting groups may be removed by hydrogenolysis under 1 to about 4 atmospheres of hydrogen in the presence of a catalyst, such as palladium on carbon. Typically, this deprotection reaction will be conducted in an inert solvent, preferably a mixture of ethyl acetate and acetic acid, at a temperature of from about 0oC to about 400C for about 1 to about 24 hours.

[112]

The poly(oxyalkylene) hydroxyaromatic ethers employed in the presem invention containing an alkyl or aralkyl ether moiety, i.e., those having the formula:

[113]

<CH2)X-(C>-CH-CH)0-OR14 (IX) 2178/37 WO 96/14371 PCr/US9S/14i72 01 wherein R %, R4, n and x are as defined above, and Ru is 02 an alkyl group or aralkyl group, may be conveniently 03 prepared from a compound of formula VIII by selectively 04 alkylating the hydroxyl group of the poly(oxyalKylene) 05 moiety of VIII with a suitable alkylating agent- 07 Typically, this alkylation reaction will be conducted by 08 first contacting VIII with a sufficient amount of a strong 09 base capable of abstracting a proton from each the hydroxyl groups present in VIII, including the aromatic hydroxyl IX group(s) and the hydroxyl group of the poly(oxyalkylene) 12 moiety. Suitable bases for this reaction include, for 13 example, sodium hydride, potassium hydride, sodium amide and 14 the like- Generally, this deprotonation reaction will be conducted in an inert solvent, such as toluene, 16 tetrahydrofuran, and the like, under substantially anhydrous 17 conditions at a temperature in the range from -10«C to 1200C 18 for about 0.25 to about 3 hours. The resulting metal salt 19 is then contacted with about 0.90 to about 1.1 molar equivalents of a suitable alkylating agent at a temperature 21 in the range from 00C to 1200c for about 1 to about 50 hours 22 to afford, after neutralization, a poly{oxyalkylene} 23 hydroxyaromatic ether of formula IX.

[114]

suitable alkylating agents for use in this reaction include 26 aikyl and aralkyl halides, such as alkyl chlorides, bromides 27 and iodides and aralkyl chlorides, bromides and iodides; and 28 alkyl and aralkyl sulfonates, such as alkyl mesylates and 29 tosylates, and aralkyl mesylates and tosylates.

[115]

31 Preferred alkylating agents are primary and secondary alkyl 32 halides having 1 to 3 0 carbon atoms, and primary and 33 secondary aralkyl halides having 7 to 36 carbon atoms; more WO 96/14371 PCT/US95/14172 01 preferred alkylating agents are primary alkyl halides having 02 4 to 12 carbon atoms.

[116]

04 Representative examples of alkylating agents include, but 05 are not limited to, methyl iodide, ethyl iodide, n-propyl 06 bromide, n-butyl bromide, n-pentyl bromide, n-hexyl 07 chloride, n-octyl chloride, n-decyl chloride, benzyl 08 chloride, and phenethyl chloride. Particularly preferred 09 alkylating agents are benzyl chloride and n-butyl bromide.

[117]

11 Alternatively, poly(oxyalkylene) hydroxyaromatic ethers of 12 formula IX may be prepared by alkylating the hydroxyl group 13 of the poly{oxyalkylene) moiety of protected intermediate 1* VII, and then deprotecting the resulting product. The conditions for alkylating intermediate VII are essentially 16 the same as those described above; however, a lesser amount 17 of base will be required since the aromatic hydroxyl groups 18 of VII are in a protected form.

[118]

other suitable methods for preparing alkyl and alkaryl 21 ethers from alcohols, and appropriate reaction conditions 22 for such reactions, can be found, for example, in I. T.

[119]

23 Harrison and S. Harrison, Compendium of Organic Synthetic 24 Methods, Vol, 1, pp. 310-312, Wiley-Interscience, New York (1971) and references cited therein.

[120]

27 The poly(oxyalkylene) hydroxyaromatic ethers employed in the 28 present invention containing a phenyl or. alkaryl ether 29 moiety, i.e., those having the formula:

[121]

31 OH 33 Rij-CCHaJjrtO-CH-CHJR (X) WO 96/14371 î / 8 73 7 PCI7US95/14172 01 wherein R %, R4, n and x are as defined above, and R is 02 a phenyl or alkaryl group, may be prepared from intermediate 03 VII in several steps by first converting the hydroxyl group 0* present on the poly(oxyaIkylene) moiety of VII into a 05 suitable leaving group, i.e., forming an intermediate having 06 -the formula:

[122]

08 OR10 09 CN 3 (CH2)x-(0-CH-CH)n-W (XI) 12 wherein Rg, R4, R10, Ru, n and x are as defined above, and W 13 is a suitable leaving group; and then displacing the leaving group of XI with a metal salt of a phenol having the formula:

[123]

OM tl6-tOJ-Rl7 OM (XII) \f i R, wherein R16 and R17 are each independently hydrogen or an alkyl group. Subseguent deprotection of the resulting product affords poly(oxyaIkylene) hydroxyaroraatic ethers of formula X.

[124]

The hydroxyl group of the poly(oxyalkylene) moiety of VII may be converted into a suitable leaving group by contacting VII with a sulfonyl chloride to form a sulfonate ester, such as a methanesulfonate (mesylate) or a toluenesulfonate (tosylate). Typically, this reaction is conducted xn the presence of a suitable amine, such as triethylarame or pyridine, in an inert solvent, such as dichloromethane, at a temperature in the range of about -10"C to about 30oC.

[125]

217873? WO 96/14371 <- ( / 0 I J ? PCT/US95/14172 01 Alternatively, the hydroxyl group of the poly(oxyalkylene) 02 moiety of VII can be exchanged for a halide, such chloride 03 or bromide, by contacting VII with a halogenating agent, 04 such as thionyl chloride, oxalyl chloride or phosphorus 05 tribromide. other suitable methods for preparing sulfonates 06 and halides from alcohols, and appropriate reaction 07 conditions for such reactions, can be found, for example, in 08 I. t. Harrison and S. Harrison, Compendium of Organic 09 Synthetic Afethods, Vol. 1, pp. 331-337, Wiley-Interscience, New York (1971) and references cited therein.

[126]

12 After forming intermediate XI, the leaving group may be 13 displaced therefrom by contacting XI with metal salt XII.

[127]

14 Generally, this reaction will be conducted in an inert solvent, such as toluene, tetrahydrofuran and the like, 16 under substantially anhydrous conditions at a temperature in 17 the range of about 250C to about 1500C for about 1 to about 18 48 hours. The metal salt XII can be formed by contacting 19 the corresponding phenol with a strong base capable of abstracting the proton from the phenolic hydroxyl group, 21 such as sodium hydride, potassium hydride, sodium amide and 22 the like, in an inert solvent.

[128]

24 Suitable phenolic compounds for use in this reaction include phenol, monoaIky1-substituted phenols and dialkyl- 26 substituted phenols. MonoaIky1-substituted phenols are 27 preferred, especially monoalkylphenols having an alkyl 28 substituent in the para position. Representative examples 29 of suitable phenolic compounds include, but are not limited to, phenol, methylphenol, dimethyIphenol, ethylphenol, 31 butyIphenol, octyIphenol, decyIphenol, dodecyIphenol, 32 tetradecyIphenol, hexadecyIphenol, octadecyIphenol, 33 eicosyIphenol, tetracosyIphenol, hexacosyIphenol, 34 triacontyIphenol and the like. Also, mixtures of WO 96/14371 PCT/US95/14172 01 alkylphenols may be employed, such as a mixture of C14-C18 02 alkylphenols, a mixture of C-c alkylphenols, a mixture of 03 C2o~c24 alkylphenols, or a mixture of C-Cjg alkylphenols.

[129]

05 Particularly preferred alkylphenols are those derived from 06 alkylation of phenol with polymers or oligomers of Cj to C6 olefins, such as polypropylene or polybutene. These polymers preferably contain 10 to 30 carbon atoms. An especially preferred alkylphenol is prepared by alkylating phenol with a propylene polymer having an average of 4 units. This polymer has the common name of propylene tetramer and is commercially available.

[130]

Alternatively, the poly(oxyalkylene) hydroxyaromatic ethers of formula X can be prepared by displacing a leaving group from an intermediate having the formula:

[131]

W- ( CH-CH-O ) n-R15 ( XIII ) 22 wherein R3, R4, Vil5 and n are as defined above, and W is a 23 suitable leaving group, with metal salt V; and then 24 deprotecting the resulting product. Conditions for this reaction are essentially the same as those described above 26 for reaction of XI with XII. Compounds of formula XIIX may 27 be prepared from XII and VI using the conditions described 28 above for the preparation of VII, followed by conversion of 29 the hydroxyl group of the poly(oxyalkylene) moiety of the resulting product into a suitable leaving using the 2i procedures described above for the preparation of XI.

[132]

WO 96/14371 <-«'U*J/ PCT/US95/14172 01 The poly(oxyalJcylene) hydroxyaromatic ethers employed in the 02 present invention containing an acyl moiety, i.e., those 03 having the formula:

[133]

06 Jv ?3 4 (CH2) -(o-CH-CH) a-O-Rj (XIV) wherein Rj, R3, 1, n and x are as defined above; and Rj is an acyl group having the formula:

[134]

12 O O II or J -0-6 -C-(CH2)u-C02R7 wherein R, R7 and u are as defined above; may be prepared from intermediate VII by first acylating the hydroxyl group of the poly(oxyalkylene) moiety of VIT to form an ester. Subsequent deprotection of the aromatic hydroxyl group(s) of the resulting ester using conventional procedures then affords poly(oxyalkylene) hydroxyaromatic ethers of formula XIV.

[135]

Generally, the acylation reaction will be conducted by contacting intermediate VTI with about 0.95 to about 1.2 molar equivalents of a suitable acylating agent.

[136]

Suitable acylating agents for use in this reaction include acyl halidss, such as acyl chlorides and bromides; and carboxylic cid anhydrides. preferred acylating agents are those having the formula: RCfO)—X, wherein R is alkyl having 1 to 3 0 carbon atom, phenyl, or aralkyl or alkaryl having 7 to 3 6 carbon atoms, and X is chloro or bromo. More preferred acylating agents are those having the formula:

[137]

WO 96/14371 2178737 PCT/US95/14172 01 EjCCOJ-X, wherein Rg is alkyl having 4 to 12 carbon atoms.

[138]

02 Representative examples of suitable acylating agents 03 include, but are not limited to, acetyl chloride, acetic 04 anhydride, propionyl chloride, butanoyl chloride, pivaloyl 05 chloride, octanoyl chloride, decanoyl chloride, 06 4-t-butylbenzoyl chloride, and the like.

[139]

08 Generally, this reaction is conducted in an inert solvent, 09 such as toluene, dichloromethane, diethyl ether and the like, at a temperature in the range of about 25"C to about 11 1500C, and is generally complete in about 0.5 to about 12 48 hours. When an acyl halide is employed as the acylating 13 agent, this reaction is preferably conducted in the presence 14 of a sufficient amount of an amine capable of neutralizing the acid generated during the reaction, such as 16 triethylamine, di(isopropyl)ethylamine, pyridine or 17 4-dimethy1am inopyr id ine.

[140]

19 Another preferred group of acylating agents are the acyl halides having the formula:

[141]

22 O 23 X-<(CK2)u-C02R7 (XV> wherein R7 is alkyl having 1 to about 10 carbon atoms, u is an integer from 1 to 10, and x is a halogen, preferably chloro or bromo.

[142]

The acyl halide of formula XV will generally be derived from a corresponding carboxylic acid having the formula:

[143]

HO-C-(CH2)u-<;02R7 (XV1) WO 96/14371 2178737 PCTAJS95/14172 wherein % and u are as defined above, by contacting the carboxylic acid of formula XVI with an inorganic acid halide, such as thionyl chloride, phosphorous trichloride, phosphorous tribromide or phosphorous pentachloride; or alternatively, with oxalyl chloride. Generally, this reaction will be conducted using about 1 to 5 molar equivalents of the inorganic acid halide or oxalyl chloride, either neat or in an inert solvent, such as diethyl ether, at a temperature in the range of about 200C to about 800C, for about l to about 48 hours. A catalyst, such as N, 11 N-dimethylformamide, may also be used in this reaction.

[144]

13 Suitable carboxylic acids of formula XVI include the mono-alkyl esters of malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid J-* and sebacic acid. Representative examples of such compounds include malonic acid mono-methyl ester, succinic acid mono-ethyl ester, adipic acid mono-methyl ester, pimelic 19 acid mono-n-butyl ester and the like. The mono-alkyl esters of these dicarboxylic acids are commercially available or 21 may be prepared by known procedures, e.g., adipic acid mono- 22 methyl ester and mono-ethyl ester are commercially available 23 from Aldrich Chemical Co., Milwaukee, Wisconsin 53233.

[145]

" Additional methods for preparing ethers from alcohols, and 26 suitable reaction conditions for such reactions, can be 27 found, for example, in I. T. Harrison and s. Harrison, Compendium of Organic Synthetic Methods, Vol. 1, pp. 273-276 and 280-283, Wiley-Interscience, New York (1971) and references cited therein.

[146]

32 Those skilled in the art will recognize that it may be 33 necessary to block or protect certain functional groups 34 while conducting the present synthetic procedures. In such WO 96/14371 2178737 PCT/US9S/14172 01 cases, the protecting group will serve to protect the 02 functional group from undesired reactions or to block its 03 undesired reaction with other functional groups or with the 04 reagents used to carry out the desired chemical 05 transformations. The proper choice of a protecting group 06 for a particular functional group will be readily apparent 07 to one skilled in the art. Various protecting groups and 08 their introduction and removal are described, for example, 09 in T. W. Greene and P. G. M. Wuts, Protective Groups in organic Synthesis, Second Edition, Wiley, New York, 1991, 11 and references cited therein.

[147]

13 m the present synthetic procedures, a hydroxyl group will 14 preferably be protected, when necessary, as the benzyl or tert-butyldimethylsilyl ether. Introduction and removal of 16 these protecting groups is well described in the art.

[148]

18 The products or product mixtures can be recovered from the 19 respective reaction product mixtures by any suitable separation and purification procedure, such as, for example, 21 extraction, evaporation, and recrystallization. Suitable 22 separation and purification procedures for recovering 23 product mixtures are, for example, illustrated in the 24 Examples set forth hereinbelow.

[149]

26 fuel Compositions 28 The compounds of the present invention are useful as 29 additives in hydrocarbon fuels to prevent and control engine deposits, particularly intake valve deposits. The proper 31 concentration of additive necessary to achieve the desired 32 deposit control varies depending upon the type of fuel 33 employed, the type of engine, and the presence of other fuel 34 additives.

[150]

WO 96/14371 *- ' ' V / *> / PCT/US95/14172 01 in general, the concentration of the Mannich condensation 02 products of this invention in hydrocarbon fuel will range 03 from about 50 to about 2500 parts per million (ppm) by 04 weight, preferably from 75 to 1000 ppm. When other deposit 05 control additives are present, a lesser amount of the 06 present additive may be used.

[151]

08 The Mannich condensation products of the present invention 09 may be formulated as a concentrate using an inert stable oleophilic (i.e., dissolves in gasoline) organic solvent 11 boiling in the range of about 150oF to 400oF (about 65cc to 12 205oC). Preferably, an aliphatic or an aromatic hydrocarbon 13 solvent is used, such as benzene, toluene, xylene or 14 higher-boiling aromatics or aromatic thinners. Aliphatic alcohols containing about 3 to 8 carbon atoms, such as 16 isopropanol, isobutylcarbinol, n-butanol and the like, in 17 combination with hydrocarbon solvents are also suitable for 18 use with the present additives. In the concentrate, the 19 amount of the additive will generally range from about 10 to about 70 weight percent, preferably 10 to 50 weight percent, 21 more preferably from 20 to 40 weight percent.

[152]

23 in gasoline fuels, other fuel additives may be employed with 24 the additives of the present invention, including, for example, oxygenates, such as t-butyl methyl ether, antiknock 26 agents, such as methylcyclopentadienyl manganese 27 tricarbonyl, and other dispersants/detergents, such as 28 hydrocarbyl amines, hydrocarbyl poly(oxyaIkylene) amines, or 29 succinimides. Additionally, antioxidants, metal deactivators and demulsifiers may be present. The gasoline 31 fuels may also contain amounts of other fuels such as, for 32 example, methanol.

[153]

WO 96/14371 *- « < v* ./( PC1YUS95/14172 -SS- 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. The diesel fuels can also include 04 other fuels such as, for example, methanol.

[154]

06 A fuel-soluble, nonvolatile carrier fluid or oil may also be 07 used with the Mannich condensation products of this 08 invention. The carrier fluid is a chemically inert 09 hydrocarbon-soluble liquid vehicle which substantially increases the nonvolatile residue (NVR), or solvent-free 11 liquid fraction of the fuel additive composition while not 12 overwhelmingly contributing to octane requirement increase.

[155]

13 The carrier fluid may be a natural or synthetic oil, such as 14 mineral oil, refined petroleum oils, synthetic polyalkanes and alkenes, including hydrogenated and unhydrogenated 16 polyalphaolefins, and synthetic polyoxyalkylene-derived 17 oils, such as those described, for example, in U.S. Patent 18 No. 4,191,537 to Lewis, and polyesters, such as those 19 described, for example, in U.S. Patent Nos. 3,756,793 and 5,004,478 to Robinson and Vogel et al., respectively, and in 21 European Patent Application Nos. 356,726 and 382,159, 22 published March 7, 1990 and August 16, 1990, respectively.

[156]

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 Mannich condensation product of this 28 invention.

[157]

The carrier fluids are typically employed in amounts ranging 31 from about 100 to about 5000 ppm by weight of the 32 hydrocarbon fuel, preferably from 400 to 3000 ppm of the 33 fuel. Preferably, the ratio of carrier fluid to deposit WO 96/1437! 2 \ 7 &7 3? PCT/US95/14172 01 control additive will range from about 0.5:1 to about 10:1, 02 more preferably from 1:1 to 4:1, most preferably about 2:1.

[158]

04 When employed in a fuel concentrate, carrier fluids will 05 generally be present in amounts ranging from about 20 to 06 about 6f- weight percent, preferably from 30 to 50 weight 07 percent 09 EXAMPLES 11 A further understanding of the invention can be had in the 12 following nonlimiting Examples. Unless expressly stated to -3 the contrary, all temperatures and temperature ranges refer 14 to the Centigrade system and the term "ambient" or "room temper ci cure" refers to about 20oC-25oC. The term "percent" 16 or %" refers to weight percent and the term "mole" or 17 "moles" refers to gram moles. The term "equivalent" refers 18 to a quantity of reagent equal in moles, to the moles of the 19 preceding or succeeding reactant recited in that example in terms of finite moles or finite weight or volume. Where 21 given, proton-magnetic resonance spectrum (p.m.r. or n.m.r.) 22 were determined at 300 mHz, signals are assigned as singlets 23 (s), broad singlets (bs), doublets (d), double doublets 24 (dd), triplets (t), double triplets (dt), quartets (q), and multiplets (m), and cps refers to cycles per second.

[159]

27 The following examples are presented to illustrate specific 28 embodiments of the present invention and synthetic 29 preparations thereof; and should not be interpreted as limitations upon the scope of the invention.

[160]

WO 96/14371 *- ' ' v I J ! PCT/US95/14172 IS 01 Example 1 03 Preparation of 04 a- f 4-BenzvloxvphenYl> -ùj-hydroxvpolv (oxvbutvlenel 06 CH2CH3 PhCHf-O-t J )--(0-CH2CH) _24-OH To a flask equipped with a magnetic stirrer, thermometer, addition funnel, reflux condenser and nitrogen inlet was added 6.88 grams of a 35 wt. % dispersion of potassium hydride in mineral oil. Forty grams of 4-benzyloxyphenol dissolved in 500 mL of anhydrous toluene was added dropwise and the resulting mixture was stirred at room temperature for ten minutes. The temperature of the reaction mixture, a thick white suspension, was raised to 90oC and 430.8 mL of 1,2-epoxybutane was added dropwise. The reaction mixture was refluxed until the pot temperature reached ILO'C (approximately 48 hours) at which time the reaction mixture was a light brown clear solution. The reaction was cooled to room temperature, quenched with 50 mL of methanol and diluted with 1 liter of diethyl ether. The resulting mixture was washed with saturated aqueous ammonium chloride, followed by water and saturated aqueous sodium chloride.

[161]

The organic layer was dried over anhydrous magnesium sulfate, filtered and the solvents removed in vacuo to yield 390 grams of a yellow oil. The oil was chromatographed on silica gel, eluting with hexane: diethyl ether (1:1), to yield 339.3 grams of the desired product as a colorless oil.

[162]

WO 96/14371 PCT/US95/14172 Example 2 03 Preparation of g-f4-Hvdr0XVPhenvl--hvdroxvpoivfoxvbutv3enP OLjCH-j H0-/Q/(C><H2CH) ~2<rOH A solution of 54.10 grams of the product from Example 1 in 100 mL of ethyl acetate and 100 mL of acetic acid containing 5.86 grains of 10% palladium on charcoal was hydrogenolyzed at 35-40 psi for 16 hours on a Parr low-pressure hydrogenator. Catalyst filtration and removal of solvent in vacuo followed by azeotropic removal of residual acetic acid with toluene under vacuum yielded 48.1 grams of the desired product as a colorless oil. The product had an average of 24 oxybutylene units. NMR (CDCL,) S 7.2 (broad s, 2H), 6.7 (s, 4H), 3.1-4.0 (m, 72H), 1.2-1.8 (m, 48H), 0.8 (t, 72H).

[163]

22 Similarly, by using the above procedures and the appropriate starting materials and reagents, the following compounds can by prepared:

[164]

26 a~ f 2"hydroxyPheny1)-w-hydroxypoly(oxybutylene); 27 a-(3-hydroxyphenyl)-o-hydroxypoly(oxybutylene) ; 28 0t~f3~t~butyl-4-hydroxyphenyl)-«-hydroxypoly(oxybutylene) ; 29 «- (4-hydroxy-3-methoxyphenyl) -a>-hydroxypoly (oxybutylene) ; a-(3,4-dihydroxyphenyl)-w-hydroxypoly(oxybutylene); 32 a~(3'4-hydroxy-5-methylphenyl) -w-hydroxypoly (oxybutylene) ; 32 ""t3'5-di-t-butyl-4-hydroxyphenyl)-w-hydroxypoly- 33 (oxybutylene); and a:-(3,4,5-trihydroxyphenyl)-oi>- 34 hydroxypoly(oxybutylene) .

[165]

WO 96/14371 t. I / U ( J ( PCTAJS95/14172 01 Example 3 03 Mannich Condensation Product of 04 a-M-HvdroxYphenyl)-w-hydroxypoly foxvbutvlene OS 06 To a flask equipped with a magnetic stirrer, thermometer, 07 reflux condensor and nitrogen inlet was added the product 08 from Example 2 (38.0 grams} and diethylene triamine (2.1 09 mL). The mixture was heated to 900C and formaldehyde (4.4 mL of a 37 weight percent solution in water) was added.

[166]

11 The reaction was heated for sixteen hours at 900C and the 12 temperature was then raised to 135"C. The reaction was 13 maintained at 1350C for two hours while sweeping out the 14 water with a stream of nitrogen. The reaction was cooled to room temperature and yielded a brown oil. The oil was 16 chromatographed on silica gel eluting with hexane/diethyl 17 ether (1:1), followed by hexane/diethyl ether/methanol/ 18 isopropylamine (4:4:1.5:0.5) to yield 22 grams of the 19 desired product as a brown oil. 1H NTCR (CDCI3, D20) S 6.4-6.75 (m, 3H), 2.2-4.0 (m, 82H), 0.6-1.75 (m, 120H).

[167]

22 Exgrople 4 24 Preparation of tt-f4-Hydroxvphenyl)-ù;-benzyloxypolyfoxvbutylene) 27 CH2CH3 -C I (0-CH2CH) _24-OCH2Ph To a flask equipped with a magnetic stirrer, thermometer, reflux condenser and nitrogen inlet was added 0.8 grams of a wt. % dispersion of potassium hydride in mineral oil.

[168]

The oil was removed by trituration with anhydrous toluene.

[169]

2!787J7 WO 96/14371 PCT/US95/14172 01 The product from Example 2 (6.0 grams} was dissolved in 02 50 mL of anhydrous tetrahydrofuran and added dropwise to the 03 potassium hydride- The reaction mixture was heated to 04 reflux for 45 minutes and then cooled to room temperature.

[170]

05 Benzyl chloride (0.36 mL) was added dropwise and the 06 reaction was then heated to reflux for 12 hours, cooled to 07 room temperature and quenched with 2 mL of isopropanol. The 08 solvent was removed in vacuo and the residue dissolved in 09 200 mL of diethyl ether, washed with 5% aqueous hydrochloric acid, followed by saturated aqueous sodium chloride. The 11 organic layer was dried over anhydrous magnesium sulfate, 12 filtered and the solvents removed under vacuum. The oil was 13 chromatographed on silica gel, eluting with hexane/ethyl 14 acetate (7:3), to yield 3.8 grams of the desired product as a colorless oil. The product had an average of 16 24 oxybutylene units. la NMR (CDCI3) S 7.2-7.4 (m, 6H) , 6.7 17 (s, 4H), 4,4-4.7 (m, 2H), 3.1-4.0 (m, 72H), 1.2-1.8 (m, « 48H), 0.8 (t, 72H).

[171]

Similarly, by using the above procedures and the appropriate starting materials and reagents, the following compounds can 22 by prepared:

[172]

a-(2-hydroxyphenyl)-u-benzyloxypoly(oxybutylene); a-(3-hydroxyphenyl)-w-benzyloxypoly(oxybutylene); 26 a-(3,4-dihydroxyphenyl)-6j-benzyloxypoly(oxybutylene) ; 27 a-(3,5-di-t-butyl-4-hydroxyphenyl)-abenzyloxy- 28 poly (oxybutylene) ; a-(4-hydroxy-3-methoxyphenyl) -cj- 29 benzyloxy-poly(oxybutylene); and a-[2-(4-hydroxyphenyl)ethyl]-w-benzyloxypoly(oxybutylene) WO 96/14371 *" ' ' w ' "t ' PCT/US95/14I72 01 Example 03 Mannich Condensation Product of 04 tt-f4-Hvdroxvphenvll-a)-benzvloxvpolvfoxvbutvlene) 06 To a flask equipped with a magnetic stirrer, thermometer, 07 reflux condenser and nitrogen inlet was added a product 08 prepared as in Example 4 (20.0 grams) and diethylene 09 triamine (1.1 mL). The mixture was heated to 90"C and X0 formaldehyde (2.2 mL of a 37 weight percent solution in 11 water) was added. The reaction was heated for sixteen hours 12 at 90oC and the temperature was then raised to 1350C. The 13 reaction was maintained at 1350C for two hours while 14 sweeping out the water with a stream of nitrogen. The reaction was cooled to room temperature and yielded a brown 16 oil. The oil was chromatographed on silica gel eluting with 17 hexane/diethyl ether (1:1), followed by hexane/diethyl 18 ether/methanol/isopropylamine (4:4:1.5:0.5) to yield 19 grams of the desired product as a brown oil. NMR (CDCI3, D2o) S 7.2-7.4 (m, 5H), 6.5-6.75 (m, 3H), 3.5-4.7 (m, 2H), 21 2.2-4.0 (m, 82H), 0.6-1.75 (m, 120H).

[173]

23 Example 6 Preparation of Methvl Adîpovl Chloride 27 To a flask equipped with a magnetic stirrer and drying tube 28 was added 7.4 mL of mono-methyl adipate and 100 mL of 29 anhydrous diethyl ether and then 21.8 mL of oxalyl chloride.

[174]

The resulting mixture was stirred at room temperature for 31 sixteen hours and then the solvent was removed in vacuo to 32 yield 8.0 grams of the desired acid chloride.

[175]

WO 96/14371 PCT/US95/14Î72 II PhCH-0 (C_) /— ( O-CICH ) _24-0-C { CH2 ) 4-C-OCH3 01 Example 7 03 Preparation of a- (4-Benzyloscyphenyl) -co- (mono-methyl 04 adipoyloxy 1 ) poly ( oxybuty lene) OS 06 CH2CH3 O O Methyl adipoyl chloride (3.57 grams) from Example 6 was combined with 42.48 grams of û!-(4-benzyloxy-phenyl)-a)- hydroxypoly(oxybutylene) from Example 1 having an average of 24 oxybutylene units and 200 mL of anhydrous toluene.

[176]

Triethylamine (3.1 mL) and 4-dimethylarainopyriâine (1.22 grams) were then added and the resulting mixture was heated to reflux under nitrogen for sixteen hours. The reaction was then cooled to room temperature and diluted with 400 mL of hexane. The organic layer was washed twice with water/ twice with saturated aqueous sodium bicarbonate solution and once with saturated aqueous sodium chloride. The organic layer was then dried over anhydrous magnesium sulfate, filtered and the solvents removed in vacuo to yield 4 0.23 grams of the desired ester.

[177]

Example 8 Preparation of a-(4-Hydroxypheny1)-«-(mono-methyl adipoyloxy)polyfoxybutylene) CH,CH, O O 31 HO <XJ) (0-CH2CH) _24-0-C (CH2) 4-0-00% 33 A solution of the ester from Example 7 (40.23 grams) in 34 100 mL of ethyl acetate and 100 mL of acetic acid containing WO 96/14371 21 7875/ PCT/US95/14172 01 5.0 grams of 10% palladium on charcoal was hydrogenolyzed at 02 35-40 psi for sixteen hours on a Parr low-pressure 03 hydrogenator. Filtration of the catalyst and removal of 04 solvent in vacuo followed by azeotropic removal of residual 05 acetic acid with toluene under vacuum yielded 36.3 grams of 06 the desired product as a colorless oil. The product had an 07 average of 24 oxybutylene units. IR (neat) 1742 cm-1; 08 % NMR (CDCLj)* 6.7 (S, 4H) , 4.7-4.8 (m, 1H) , 3.0-4.0 09 (m, 75H) , 2.2(t, 4H) , 0.6-1.7(iti, 124H) .

[178]

11 Example 9 13 Mannich Condensation Product of a- (4-Hydroxyphenyl)-a3-(mono- H methvlad jpovioxv) poly f oxybutylene ) 16 To a flask equipped with a magnetic stirrer, thermometer, 17 reflux condenser and nitrogen inlet was added the product 18 from Example 8 (15.0 grams) and diethylene triamine 19 (0.9 mL). The mixture was heated to 900C and formaldehyde (0.7 mL of a 37 weight percent solution in water) was added.

[179]

21 The reaction was heated for sixteen hours at 90oC and the 22 temperature was then raised to 1350C. The reaction was 23 maintained at 1350C for two hours while sweeping out the 2* water with a stream of nitrogen. The reaction was cooled to room temperature and yielded a brown oil. The oil was 26 chromatographed on silica gel eluting with hexane/diethyl 27 ether (1:1), followed by hexane/diethyl 28 ether/methanol/isopropylamine (4:4:1.5:0.5) to yield 9 grams 29 of the desired product as a brown oil. IR (neat) 1742cin~1; NMR (CDC13/ D20) S 6.4-6.75 (m, 3H) , 4.75-4.9 (m, 1H) , 31 2.3-4.0 (m, 84H), 2.25 (t, 4H), 0.6-1.75 (m, 124H).

[180]

WO 96/14371 PCT7US95/14n2 01 Example 03 Sinqle-Cvlinder Engine Test 05 The test compounds were blended in gasoline and their 06 deposit reducing capacity determined in an ASTM/CFR 07 single-cylinder engine test.

[181]

09 A Waukesha CFR single-cylinder engine was used. Each run was carried out for 15 hours, at the end of which time the 11 intake valve was removed, washed with hexane and weighed.

[182]

12 The previously determined weight of the clean valve was 13 subtracted from the weight of the value at the end of the 14 run. The differences between the two weights is the weight of the deposit. A lesser amount of deposit indicates a 16 superior additive. The operating conditions of the test 17 were as follows: water jacket temperature 200oF; vacuum of 18 12 in Hg, air-fuel ratio of 12, ignition spark timing of 19 40° BTC; engine speed is 1800 rpra; the crankcase oil is a commercial 30W oil.

[183]

22 The amount of carbonaceous deposit in milligrams on the 23 intake valves is reported for each of the test compounds in 24 Table I. (Reference to a compound by Example No. refers to the title composition for that Example.) WO 96/14371 2Î78737 PCT/ÎJS95/14172 Table I Intake Valve Deposit Weight (in milligrams) Sample1 Run 1 Run 2 Average Base Fuel Example 3 Example Example 9 297.0 0.4 0.0 49.7 280.4 10.0 0.0 60.3 288.7 5.2 0.0 55.0 IAt 200 parts per million actives (ppma).

[184]

The base fuel employed in the above single-cylinder engine tests was a regular octane unleaded gasoline containing no fuel detergent. The test compounds were admixed with the base fuel to give a concentration of 200 ppma (parts per million actives).

[185]

The data in Table I illustrates the outstanding reduction in intake valve deposits provided by the Mannich condensation product of the present fuel additive composition compared to the base fuel.

[186]

Obviously, many modifications and variations of the invention described hereinabove and below can be made without departing from the essence and scope thereof.

[187]

WO 96/14371 PCr/US95/14172 01 WHAT IS CLAIMED IS:

[188]

03 1. A composition prepared by the Mannich condensation of a 04 compound of the formula:

[189]

06 OH 07 J. S3 «4 08 Rj-fQH-tCHCO-CH-CHJ-O- * atoms ; wherein Rj is hydrogen, hydroxy, lower alkyl having 1 to 6 carbon atoms, or lower alkoxy having 1 to 6 carbon R3 and R4 are each independently hydrogen or lower alkyl having 1 to 6 carbon atoms; R5 is hydrogen, alkyl having 1 to 30 carbon atoms, phenyl, aralkyl or alkaryl having 7 to 3 6 carbon atoms, or an acyl group having the formula:

[190]

O O 22 I or || 23 -Q-JR6 -CMCH2)u-C02R7 wherein R is alkyl having 1 to 3 0 carbon atoms, 26 phenyl, or aralkyl or alkaryl having 7 to 36 carbon 27 atoms; R7 is alkyl having 1 to about 10 carbon atoms; 28 and u is an integer from 1 to 10; n is an integer from 5 to 100; and x is an integer from 31 0 to 10; 33 with an aldehyde having the formula HR2C(0) , wherein 1 34 is hydrogen or lower alkyl having 1 to 6 carbon atoms.



Mannich condensation products prepared by the condensation of a compound of formula (XIV), wherein R1 is hydrogen, hydroxy, lower alkyl or lower alkoxy; R3 and R4 are independently hydrogen or lower alkyl; R5 is hydrogen, alkyl, phenyl, aralkyl, alkaryl, or an acyl group of formulae (a) or (b) wherein R6 is alkyl, phenyl, aralkyl or alkaryl; R7 is alkyl; u is an integer from 1 to 10; n is an integer from 5 to 100; and x is an integer from 0 to 10; with an aldehyde and a nitrogen base selected from ammonia, lower alkylamine, a polyamine and mixtures thereof. The Mannich condensation products and their fuel soluble salts are useful as fuel additives for the prevention and control of engine deposits.



WO 96/14371 PCr/US95/14172 01 WHAT IS CLAIMED IS: 03 1. A composition prepared by the Mannich condensation of a 04 compound of the formula: 06 OH 07 J. S3 «4 08 Rj-fQH-tCHCO-CH-CHJ-O- * atoms ; wherein Rj is hydrogen, hydroxy, lower alkyl having 1 to 6 carbon atoms, or lower alkoxy having 1 to 6 carbon R3 and R4 are each independently hydrogen or lower alkyl having 1 to 6 carbon atoms; R5 is hydrogen, alkyl having 1 to 30 carbon atoms, phenyl, aralkyl or alkaryl having 7 to 3 6 carbon atoms, or an acyl group having the formula: O O 22 I or || 23 -Q-JR6 -CMCH2)u-C02R7 wherein R is alkyl having 1 to 3 0 carbon atoms, 26 phenyl, or aralkyl or alkaryl having 7 to 36 carbon 27 atoms; R7 is alkyl having 1 to about 10 carbon atoms; 28 and u is an integer from 1 to 10; n is an integer from 5 to 100; and x is an integer from 31 0 to 10; 33 with an aldehyde having the formula HR2C(0) , wherein 1 34 is hydrogen or lower alkyl having 1 to 6 carbon atoms. ?i78737 WO 96/14371 L * PCT/DS95/14172 01 and a nitrogen base selected from ammonia, lower 02 alkylamine having 1 to 6 carbon atoms, a polyamine 03 having 2 to about 12 amine nitrogen atoms and 2 to 04 about 40 carbon atoms and mixtures thereof. 06 2. The composition according to Claim 1, wherein n is an 07 integer ranging from 10 to 50. 09 3. The composition according to Claim 2, wherein n is an integer ranging from 15 to 30. il 12 4. The composition according to Claim 2, wherein 1 is 13 hydrogen, hydroxy, or lower alkyl having 1 to 4 carbon 14 atoms; and said nitrogen base is a polyalkylene _ polyamine. 17 5. The composition according to Claim 4, wherein R5 is 18 hydrogen, alkyl having 1 to 24 carbon atoms, or I' alkylphenyl or phenylalkyl having an alkyl group containing 1 to 24 carbon atoms. 22 6. The composition according to Claim 5, wherein is 23 hydrogen or hydroxy, and said nitrogen base is a 24 polyethylene polyamine or a polypropylene polyamine. 26 7. The composition according to Claim 6, wherein R5 is 27 hydrogen, alkyl having 4 to 12 carbon atoms, or 28 alkylphenyl or phenylalkyl having an alkyl group 29 containing 1 to 12 carbon atoms. 31 8. The composition according to Claim 7, wherein one of R3 32 and R4 is lower alkyl having 1 to 3 carbon atoms and the other is hydrogen. i 2178737 WO 96/14371 PCT/US95/14172

9. The composition according to Claim 8, wherein one of R3 and 1*4 is methyl or ethyl and the other is hydrogen.

10. The composition according to Claim 9, wherein x is 0, l or 2.

11. The composition according to Claim 10, wherein 1 is hydrogen, % is alkylphenyl or phenylalkyl having an alkyl group containing 1 to 12 carbon atoms, x is 0, and said nitrogen base is ethylene diamine or diethylene triamine.

12. A compound of the formula: 19 -C R3 R4 atoms; (CH2Ï x-(0~CBr-CE) n-OR5 wherein Rj is hydrogen, hydroxy, lower alkyl having 1 to 6 carbon atoms, or lower alkoxy having 1 to 6 carbon R2 is hydrogen or lower alkyl having 1 to 6 carbon atoms; R3 and R4 are each independently hydrogen or lower alkyl having 1 to 6 carbon atoms; WO 96/14371 2178737 PCT/US95/14172 01 % is hydrogen, alkyl having 1 to 30 carbon atoms, 02 phenyl, aralkyl or alkaryl having 7 to 3 6 carbon atoms, 03 or an acyl group having the formula: 05 0 O -è- -<v_(CH2)u-C02R7 wherein 1 is alkyl having 1 to 30 carbon atoms, phenyl, or aralkyl or alkaryl having 7 to 36 carbon atoms; R7 is alkyl having 1 to about 10 carbon atoms; and u is an integer from 1 to 10; n is an integer from 5 to 100; and x is an integer from 0 to 10; and Y is selected from amino, lower alkylamino having 1 through 6 carbon atoms or a polyamine radical having 2 through 12 amine nitrogen atoms and 2 through 40 carbon atoms; wherein the attachment of Y to the -01%- 1inking group is through one of its amine nitrogen atoms.

13. The compound according to Claim 12, wherein n is an integer ranging from 10 to 50.

14. The compound according to Claim 13, wherein n is an integer ranging from 15 to 30.

15. The compound according to Claim 13, wherein Rj is hydrogen, hydroxy, or lower alkyl having 1 to 4 carbon atoms; and Y is a polyalkylene polyamine radical. WO 96/14371 PCT/US95/14I72 01 16. The compound according to Claim 15, wherein % is 02 hydrogen, alkyl having 1 to 24 carbon atoms, or 03 alkylphenyl or phenylalkyl having an alkyl group 04 containing 1 to 24 carbon atoms. 06 17. The compound according to Claim 16, wherein is 07 hydrogen or hydroxy, and Y is a polyethylene polyamine 08 radical or a polypropylene polyamine radical.

18. The compound according to Claim 17, wherein Rj is hydrogen, alkyl having 4 to 12 carbon atoms, or alkylphenyl or phenylalkyl having an alkyl group containing 1 to 12 carbon atoms.

19. The compound according to Claim 18, wherein one of Eg and R4 is lower alkyl having 1 to 3 carbon atoms and the other is hydrogen.

20. The compound according to Claim 19, wherein one of R3 and R4 is methyl or ethyl and the other is hydrogen.

21. The compound according to Claim 20, wherein x is 0, 1 or 2.

22. The compound according to Claim 21, wherein Ri is hydrogen, Rj is alkylphenyl or phenylalkyl having an alkyl group contahjrtg 1 to 12 carbon atoms, x is 0, and Y is an ethyleire> diamine radical or a diethylene triamine radical.

23. A fuel composition comprising a major amount of hydrocarbons boiling in the gasoline or diesel range and an effective deposit-controlling amount of a WO 96/14371 21 78737 PCT/US95/14172 01 composition prepared by the Mannich condensation of a 02 compound of the formula: 04 OH 1 -rOj- {CE x-f0"111) n-0" 06 R 08 wherein fy is hydrogen, hydroxy, lower alkyl having 1 09 to 6 carbon atoms, or lower alkoxy having 1 to 6 carbon atoms; 12 R3 and i are each independently hydrogen or lower 13 alkyl having 1 to 6 carbon atoms; Rj is hydrogen, alkyl having 1 to 3 0 carbon atoms, 16 phenyl, aralkyl or alkaryl having 7 to 3 6 carbon atoms, 17 or an acyl group having the formula: 19 O 0 J or || -G-j -0-(CH2)u-6C02R7 wherein F is alkyl having 1 to 3 0 carbon atoms, phenyl, or aralkyl or alkaryl having 7 to 36 carbon atoms; R7 is alkyl having 1 to about 10 carbon atoms; 26 and u is an integer from 1 to 10; 28 n is an integer from 5 to 100 ; and x is an integer from 29 0 to 10; with an aldehyde having the formula HICCO) r wherein R2 is hydrogen or lower alkyl having 1 to 6 carbon atoms, 33 and a nitrogen base selected from ammonia, lower 34 alkylamine having 1 to 6 carbon atoms, a polyamine 218737 WO96/14371 ' i vi j/ PCT/US95/14172 01 having 2 to about 12 amine nitrogen atoms and 2 to 02 about 40 carbon atoms and mixtures thereof. 04 24. The fuel composition according to Claim 23, wherein 05 is hydrogen, hydroxy, or lower alkyl having 1 to 4 carbon atoms; one of R3 and R4 is hydrogen and the other is methyl or ethyl; % is hydrogen, alley 1 having l to 24 carbon atoms, or alkylphenyl or phenylalkyl having an alkyl group containing 1 to 24 carbon atoms; n is 15 to 30; x is 0, 1 or 2; and said nitrogen base is a polyalkylene polyamine. oe

25. The fuel composition according to Claim 24, wherein Rj is hydrogen or hydroxy; R5 is hydrogen, alkyl having 1 to 12 carbon atoms, or alkylphenyl or phenylalkyl having an alkyl group containing 1 to 12 carbon atoms; x is 0; and said nitrogen base is a polyethylene polyamine or a polypropylene polyamine.

26. The fuel composition according to Claim 25, wherein is hydrogen, % is alkylphenyl or phenylalkyl having an alkyl group containing 1 to 12 carbon atoms, and said nitrogen base is ethylene diamine or diethylene triamine.

27. 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: WO 96/14371 21 78757 PCT/US95/14172 05 \ I I 06 X(CH2)x-(0-CS-CH)I1-OE5 08 wherein is hydrogen, hydroxy, lower alkyi having 1 09 to 6 carbon atoms, or lower alkoxy having 1 to 6 carbon atoms; 12 r2 is hydrogen or lower alkyl having 1 to 6 carbon 13 atoms; r3 and R4 are each independently hydrogen or lower 16 alkyl having 1 to 6 carbon atoms; 18 Rj is hydrogen, alkyl having 1 to 30 carbon atoms, phenyl, aralkyl or alkaryl having 7 to 3 6 carbon atoms, or an acyl group having the formula: 22 o o 23 11 or H 24 -c-Re -o-(ch2)u-<:o2r7 29 and vl is an integer from 1 to 10; 3! n is an integer from 5 to 100; and x is an integer from 32 0 to 10; and wherein R is alkyl having l to 30 carbon atoms, phenyl, or aralkyl or alkaryl having 7 to 36 carbon atoms; R7 is alkyl having 1 to about 10 carbon atoms; WO 96/14371 PCT/US95/14172 01 Y is selected from amino, lower alkylamino having 1 02 through 6 carbon atoms or a polyamine radical having 2 03 through 12 amine nitrogen atoms and 2 through 40 carbon 04 atoms; wherein the attachment of Y to the -CHRj- 05 linking group is through one of its amine nitrogen 06 atoms. 08 28. The fuel composition according to Claim 27, wherein fy is hydrogen, hydroxy, or lower alkyl having 1 to 4 carbon atoms; one of R3 and R4 is hydrogen and the other is methyl or ethyl; R5 is hydrogen, alkyl having 1 to 24 carbon atoms, or alkylphenyl or phenylalkyl having an alkyl group containing 1 to 24 carbon atoms; n is 15 to 30; x is 0, 1 or 2; and Y is a polyalkylene polyamine radical. IS 1»

29. The fuel composition according to Claim 28, wherein Rj is hydrogen or hydroxy; R5 is hydrogen, alkyl having 4 to 12 carbon atoms, or alkylphenyl or phenylalkyl having an alkyl group containing 1 to 12 carbon atoms; x is 0; and Y is a polyalkylene polyamine radical.

30. The fuel composition according to Claim 29, wherein Rj is hydrogen, R5 is alkylphenyl or phenylalkyl having an alkyl group containing 1 to 12 carbon atoms, and Y is an ethylene diamine radical or a diethylene triamine radical.

31. A fuel concentrate comprising an inert stable - oleophilic organic solvent boiling in the range of from about 150oF to 400oF and from about 10 to about 70 weight percent of a composition prepared by the Mannich condensation of a compound of the formula: WO «14371 PCTnjS9S/14172 -SS¬ CI OH 03 RlJX(CH2)3r(0-CH-CH)irOHR5 05 wherein % is hydrogen, hydroxy, lower alkyl having 1 06 to 6 carbon atoms, or lower alkoxy having 1 to 6 carbon 07 atoms; 09 Rj and R4 are each independently hydrogen or lower alkyl having l to 6 carbon atoms; 12 Rj is hydrogen, alkyl having 1 to 30 carbon atoms, 13 phenyl, aralkyl or alkaryl having 7 to 36 carbon atoms, 14 or an acyl group having the formula: 16 0 9 ' 17 II or -o-a, -<-(ch2)u-<:o2r7 18 26 0 to 10' wherein 1 is alkyl having 1 to 30 carbon atoms, phenyl, or aralkyl or alkaryl having 7 to 36 carbon atoms; R7 is alkyl having 1 to about 10 carbon atoms; and u is an integer of from 1 to 10; n is an integer from 5 to 100; and x is an integer from with an aldehyde having the formula HR2C(0) , wherein R is hydrogen or lower alkyl having 1 to 6 carbon atoms, and a nitrogen base selected from ammonia, lower alkylamine having 1 to 6 carbon atoms, a polyamine having 2 to about 12 amine nitrogen atoms and 2 to about 40 carbon atoms and mixtures thereof. i 2Î78737 WO 96/14371 PCT/US95/14172 01 32- The fuel concentrate according to Claim 31, wherein Rj 02 is hydrogen, hydroxy, or lower alkyl having 1 to 03 4 carbon atoms; one of R3 and 1 is hydrogen and the 04 other is methyl or ethyl; 1 is hydrogen, alkyl having 1 to 24 carbon atoms, or alkylphenyl or phenylalkyl having an alkyl group containing 1 to 24 carbon atoms; n is 15 to 30; x is 0, 1 or 2; and said nitrogen base is a polyalkylene polyamine.

33. The fuel concentrate according to Claim 32, wherein is hydrogen or hydroxy; R5 is hydrogen, alkyl having 4 to 12 carbon atoms, or alkylphenyl or phenylalkyl having an alkyl group containing 1 to 12 carbon atoms; x is 0; and said nitrogen base is a polyethylene polyamine or a polypropylene polyamine.

34. The fuel concentrate according to Claim 33, wherein is hydrogen, Rj is alkylphenyl or phenylalkyl having an alkyl group containing 1 to 12 carbon atoms, and said nitrogen base is ethylene diamine or diethylene triamine.

35. A fuel concentrate comprising an inert stable oleophilic organic solvent boiling in the range of from about 150eF to 400oF and from about 10 to about " ". weight percent of a compound of the formula: WO96/14371 t. I / U / *>' PCT/US95/14172 fî4 06 (CH2)x-(a-CH-CH)irOR5 08 wherein Rj is hydrogen, hydroxy, lower alkyl having 1 09 to 6 carbon atoms, or lower alkoxy having 1 to 6 carbon atoms; 12 R2 is hydrogen or lower alkyl having 1 to 6 carbon 13 atoms; R3 and R are each independently hydrogen or lower 16 alkyl having 1 to 6 carbon atoms; 18 Ilj is hydrogen, alkyl having 1 to 30 carbon atoms, 19 phenyl, araIky1 or alkaryl having 7 to 3 6 carbon atoms, or an acyl group having the formula: 22 o O II or |j -O-Rfi -0-(CH2)u-C02R7 wherein R is alkyl having 1 to 30 carbon atoms, phenyl, or aralkyl or alkaryl having 7 to 3 6 carbon atoms; R7 is alkyl having 1 to about 10 carbon atoms; and u is an integer from 1 to 10; n is an integer from 5 to 100; and x is an integer from 0 to 10; and WO 96/14371 PCmJS95/14172 01 Y is selected from amino, lower alkylami.no having 1 through 6 carbon atoms or a polyamine radical having 2 03 through 12 amine nitrogen atoms and 2 through 40 carbon 04 atoms; wherein the attachment of Y to the -CHI- linking group is through one of its amine nitrogen 06 atoms.

36. The fuel concentrate according to Claim 35, wherein Rj is hydrogen, hydroxy, or lower alkyl having 1 to .4 carbon atoms; one of R3 and R4 is hydrogen and the other is methyl or ethyl; R5 is hydrogen, alkyl having 1 to 24 carbon atoms, or alkylphenyl or phenylalkyl having an alkyl group containing 1 to 24 carbon atoms; n is 15 to 30; x is 0, 1 or 2; and Y is a polyalkylene polyamine radical.

37. The fuel concentrate according to Claim 36, wherein R1 is hydrogen or hydroxy; R3 is hydrogen, alkyl having 4 to 12 carbon atoms, or alkylphenyl or phenylalkyl having an alkyl group containing 1 to 12 carbon atoms; x is 0; and Y is a polyethylene polyamine radical or a polypropylene polyamine radical.

38. The fuel concentrate according to Claim 37, wherein B. is hydrogen, R5 is alkylphenyl or phenylalkyl having an alkyl group containing l to 12 carbon atoms, and Y is an ethylene diamine radical or a diethylene triamine radical.