U. S. Pat No. 4, 382, 006 describes ethoxylated amines and borated derivatives thereof useful as friction modifying additives for organic fluids. U. S. Pat No. 4,406, 802 teaches borates of mixed alcohols, amides, amines, hydroxy esters, ethoxylated amines, ethoxylated amides and hydroxyalkyl, hydroxyalkenylalkyl or alkenylimidazolines.

U. S. Pat No. 4,389, 322 discloses ethoxylated amides and borated adducts thereof as friction reducing additives. U. S. Pat No. 4,568, 472 provides multifunctional additives for lubricating media, which are borates of mixed ethoxylated amines and amides, hydroxyalkyl imidazol- nes, hydrolyzed hydroxyalkyl imidazolines and hydroxyesters.

U. S. Pat. No. 4,492, 642 teaches lubricant additives which are the product of reacting a bor- ating agent with an ammoniated hydrocarbyl epoxide.

U. S. Pat. No. 4, 892, 670 discloses boron-containing heterocyclic compounds prepared by re- acting a primary amine or ammonia with an alkylen oxide or epoxide and then concurrently or subsequently the intermediate is reacted with a boric acid. The compounds are suitable antiwear additives for lubricating compositions.

U. S. Pat No. 4, 741, 848 teaches boron containing compounds prepared by reacting hydroxy substituted esters, amides or imides with boric acid, boron trioxide, boron halides, boron amides or boron esters. The boron compounds are used as additives in lubricants and fuels. <BR> <BR> <P>Yao, J. and Dong, J. Lubr. Eng. 1995, 51 (6), 475-8 and Zheng, Z. , et al., Wear 1998,222, 135-144) alkyl borates that contain nitrogen into the molecular structure.

It has been found that borates and boronate esters derived from 2-hydroxyethylpyridines, bo- ric acids or boronic acids and hydrocarbyl alcohols provide excellent antiwear, extreme pres- sure, and friction modifying additives for lubricating oils and fuels.

Disclosed are borate and boronate compounds of the formulae

wherein Ri, R2 and R3 are independently hydrogen, straight or branched chain alkyl of 1 to 24 carbon atoms, straight or branched chain alkenyl of 2 to 24 carbon atoms, cycloalkyl of 5 to 12 car- bon atoms, aryl of 6 to 10 carbon atoms, aralkyl of 7 to 15 carbon atoms, alkaryl of 7 to 15 carbon atoms; Ar is substituted or unsubstituted aryl of 6 to 10 carbon atoms, and R4 and R5 are independently defined as for Ri and may also be hydroxyphenyl or alkylated hydroxyphenyl, or R4 and Rs together with the-OBO-group form a substituted or unsubstituted 5 or 6 mem- bered ring.

For example, Ri, R2, R3, R4 and R5 are independently hydrogen or straight or branched chain alkyl of 1 to 24 carbon atoms, aryl of 6 to 10 carbon atoms or alkaryl of 7 to 15 carbon atoms.

For instance, R4 and R6 are independently n-butyl, sec-butyl, t-butyl, n-dodecyl, n-octadecyl, n-octyl, isooctyl, oleyl, stearyl, n-tetradecyl, 1-hexadecyl, linoleyl, linolenyl, phytyl, myricyl, lauryl, myristyl, cetyl, behenyl, phenyl, catechyl, alkylated phenyl or alkylated hydroxyphenyl.

When R4 and R5 together with the-OBO-group form a substituted or unsubstituted 5 or 6 membered ring, the substituent is for example alkyl of 1 to 6 carbon atoms or is hydroxy. The ring may be substituted for example by 1 to 4 such groups.

Alkyl is straight or branched chain and is for example methyl, ethyl, n-propyl, iso-propyl, n- butyl, isobutyl, sec-butyl, t-butyl, n-pentyl, isopentyl, n-hexyl, n-heptyl, 3-heptyl, n-octyl, 2- ethylhexyl, n-nonyl, n-decyl, undecyl, n-dodecyl, tridecyl, n-tetradecyl, pentadecyl, n-hexade- cyl, n-octadecyl, n-eicosyl, heptadecyl, 2-ethylbutyl, 1-methylpentyl, 1, 3-dimethylbutyl, 1,1, 3, 3-tetramethylbutyl, 1-methylhexyl, isoheptyl, 1-methylheptyl, 1,1, 3-trimethylhexyl and 1- methylundecyl.

Alkenyl is straight or branched chain and is unsaturated version of alkyl, for example allyl, prop-2-enyl, but-2-enyl, 2-methyl-prop-2-enyl, pent-2-enyl, hexa-2, 4-dienyl, dec-10-enyl or eicos-2-enyl.

Cycloalkyl is, for example, cyclopentyl, methylcyclopentyl, dimethylcyclopentyl, cyclohexyl, methylcyclohexyl, dimethylcyclohexyl, trimethylcyclohexyl, tert-butylcyclohexyl, cyclodecyl, adamantyl, cyclododecyl, cycloheptyl or cyclooctyl.

Aralkyl is for example benzyl, a-methylbenzyl, a, a-dimethylbenzyl or 2-phenylethyl.

Aryl is for example phenyl or naphthyl. Substituted aryl is for example aryl substituted by 1 to 4 alkyl of 1 to 6 carbon atoms or hydroxy groups.

Alkaryl is for example o-, m-or p-methylphenyl, 2, 3-dimethylphenyl, 2, 4-dimethylphenyl, 2,5- dimethylphenyl, 2, 6-dimethylphenyl, 3, 4-dimethylphenyl, 3, 5-dimethylphenyl, 2-methyl-6-eth- ylphenyl, 4-tert-butylphenyl, 2-ethylphenyl, 2, 6-diethylphenyl, 2, 4-di-t-butylphenyl or 2,6-di-t- butyl-4-methylphenyl.

Hydroxyphenyl is for example 3-hydroxyphenyl.

Alkylated hydroxyphenyl is for example mono-or di-alkylated 3-hydroxyphenyl, for example 2-methyl-3-hydroxyphenyl, 4-methyl-3-hydroxyphenyl, 2-ethyl-3-hydroxyphenyl, 4-ethyl-3-hy- droxyphenyl, 2-t-butyl-3-hydroxyphenyl, 4-t-butyl-3-hydroxyphenyl, 2-hexyl-3-hydroxyphenyl, 4-hexyl-3-hydroxyphenyl, 2, 4-dimethyl-3-hydroxyphenyl, 2-methyl-4-t-butyl-3-hydroxyphenyl, and the other corresponding dialkylated versions. That is, the present compounds may be prepared with resorcinol or alkylated resorcinol.

According to a preferred embodiment the invention relates to a compound of the formula (I) or (II) selected from the group consisting of di-n-dodec-1-yl-2-(pyrid-2-yl) ethyl borate, n-oc- tadec-1-yl-2- (pyrid-2-yl) ethyl phenylboronate, n-oct-1-yl-2- (pyrid-2-yl) ethyl phenylboronate and n-ole-1-yl-2-(pyrid-2-yl) ethyl phenylboronate.

The present compounds are for example prepared by the reaction of 2-hydroxyethylpyridi- nes, boric acids or boronic acids and hydrocarbyl alcohols. For example, a present borate is prepared by the reaction of 2-hydroxyethylpyridine with boric acid and two equivalents of a hydrocarbyl alcohol, under conditions in which water is azeotropically removed. In a typical reaction, 1 equivalent of 2- (2-hydroxyethyl) pyridine, 2 equivalents of an alkanol (for example straight or branched chain C4-C,8alkyl alcohol) and 1 equivalent of boric acid are heated to- gether in an inert solvent under conditions such that water is azeotropically removed.

Boronates are similarly prepared, for example from the reaction of 2- (2-hydroxyethyl) pyri- dine, an arylboronic acid and 1 equivalent of an alkanol under conditions of the removal of water.

According to a preferred embodiment a mixture of alkanols may be employed.

The solvent employed is for example toluene, xylene and the like. It is contemplated that un- der suitable conditions that the reaction may be run neat (no solvent).

Hydrocarbyl alcohols are for example 1-butanol, sec-butanol, t-butanol, 1-dodecanol, 1-octa- decanol, 1-octanol, isooctanol, oleyl alcohol, stearic alcohol, 1-tetradecanol, 1-hexadecanol, linoleyl alcohol, linolenyl alcohol, phytol, myricyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, behenyl alcohol, phenol, catechol, alkylated phenols, alkylated rescorcinols, ethyl- ene glycol, propylene glycol, and the like.

The arylboronic acid is for example phenylboronic acid and the like.

Also subject of the present invention is a lubricant composition having improved antiwear properties comprising a) A lubricating oil ; and b) An antiwear enhancing amount of at least one compound of the formula (I) or (II), wherein Ri, R2, R3, R4 and R5 are as defined above.

The lubricating oils according to the invention are for example those employed in internal combustion engines. The present oils have necessary lubricating viscosity. The oils are for example mineral oils or are synthetic and mixtures thereof.

Greases or other solid lubricants are also lubricating oils according to this invention.

The synthetic hydrocarbon oils include long chain alkanes such as cetanes and olefin poly- mers such as trimer and tetramers of octane and decene. These synthetic oils can be mixed with 1) ester oils such as pentaerythritol esters of monocarboxylic acids having about 2 to 20 carbon atoms, 2) polyglycol ethers, 3) polyacetals and 4) siloxane fluids. Useful among the synthetic esters are those made from polycarboxylic acids and monohydric alcohols. For ex- ample, ester fluids made from pentaerythritol or mixtures thereof with di-and tripentaerythri- tol, and an aliphatic monocarboxylic acid containing from 1 to 20 carbon atoms, or mixtures of such acids. Other examples are ester fluids made from trimethylolpropane and an aliphatic monocarboxylic acid containing from 1 to 20 carbon atoms, or mixtures of such acids.

The present lubricating oils are also for example crude oil, industrial lubrication oils, cutting oil, metal working fluids and greases.

Another use for the present borate and boronate addititives is in fuels, for example certain aviation fuels and the like, wherein lubrication properties are desired. The fuels are for ex- ample a hydrocarbonaceous petroleum distillate such as motor gasoline, diesel fuel or fuel oil. Liquid fuel compositions comprising non-hydrocarbonaceous materials such as alcohols, ethers, organo-nitro compounds and the like (e. g. methanol, ethanol, diethyl ether, methyl ethyl ether, nitromethane) are also within the scope of this invention as are liquid fuels de- rived from vegetable or mineral sources such as corn, alfalfa, shale and coal. Fuels, which are mixtures of one or more hydrocarbonaceous fuels and one or more non-hydrocarbona- ceous materials, are also contemplated. Examples of such mixtures are combinations of gasoline and ethanol and of diesel fuel and ether.

The present additives provide extreme pressure, antiwear and friction reducing properties to the oil, and upon combustion, are innocuous to conventional catalytic converters in automo- biles.

The additives of this invention are advantageously present in the oil composition in an amount of for example about 0. 01 % to about 20% by weight of the total composition. For in- stance, the borates and boronates are present from about 0. 05% to about 15%, from about 0. 1 % to about 10%, from about 0.2% to about 5% by weight, based on the weight of the en- tire composition. For example, the borates and boronates are present from about 0.1 % to about 20%, from about 0. 1 % to about 15% or from about 0. 1 % to about 5% by weight, based on the weight of the entire composition.

It is contemplated that in lubricating compositions operated under extremely adverse condi- tions, such as lubricating compositions for marine diesel engines, that the additives of this in- vention may be present in amounts of up to about 30% by weight, or more, of the total weight of the lubricating composition.

The additives of this invention are advantageously present in the fuel compositions at a level of from about 1 ppm to about 50,000 ppm based on the fuel. For example the additives are present from about 4 ppm to about 5000 ppm based on the fuel.

The lubricating oils stabilized in accordance with the invention may additionally include other additives, which are added in order to improve still further the basic properties of these for- mulations ; such additives include antioxidants, metal passivators, rust inhibitors, corrosion inhibitors, viscosity index improvers, extreme pressure agents, pour point depressants, solid lubricants, dispersants, detergents, antifoams, color stabilizers, further high-pressure addi- tives, demulsifiers, antiwear additives and additives which reduce the coefficient of friction.

Such additives are added in the customary amounts in each case in the range from in each case about 0. 01 % to 10.0% by weight, based on the lubricating oil.

The text below gives examples of such additional additives: 1 Examples of antioxidants: 1. 1 Alkylated monophenols, for example 2, 6-di-tert-butyl-4-methylphenol, 2-butyl-4, 6- dimethylphenol, 2, 6-di-tert-butyl-4-ethylphenol, 2, 6-di-tert-butyl-4-n-butylphenol, 2,6-di- tert-butyl-4-iso-butylphenol, 2, 6-di-cyclopentyl-4-methylphenol, 2- (a-methyl-cyclohexyl)- 4, 6-dimethylphenol, 2, 6-di-octadecyl-4-methylphenol, 2,4, 6-tri-cyclo-hexylphenol, 2,6-di- tert-butyl-4-methoxymethylphenol, linear or side-chain-branched nonylphenols, for exam- ple 2, 6-di-nonyl-4-methylphenol, 2, 4-dimethyl-6- (1'-methyl-undec-1'-yl) phenol, 2,4-di- methyl-6- (1'-methylheptadec-1'-yl) phenol, 2, 4-dimethyl-6- (1'-methyltridec-1'-yl) phenol or mixtures thereof 1. 2 Alkylthiomethylphenols, for example 2, 4-di-octylthiomethyl-6-tert-butylphenol, 2, 4-di-octyl- thiomethyl-6-methylphenol, 2, 4-di-octylthiomethyl-6-ethylphenol or 2, 6-di-dodecyl- thiomethyl-4-nonylphenol 1. 3 Hydroquinones and alkylated hydroquinones, for example 2, 6-di-tert-butyl-4-methoxyphe- nol, 2, 5-di-tert-butylhydroquinone, 2, 5-di-tert-amylhydroquinone, 2, 6-diphenyl-4-octade- cyloxyphenol, 2, 6-di-tert-butyl-hydroquinone, 2, 5-di-tert-butyl-4-hydroxyanisole, 3,5-di- tert-butyl-4-hydroxyanisole, 3, 5-di-tert-butyl-4-hydroxyphenyl stearate or bis (3,5-di-tert- butyl-4-hydroxyphenyl) adipate 1. 4 Tocopherols, for example a-, P-, y-or 8-tocophero) or mixtures thereof (vitamin E) 1. 5 Hvdroxylated thiodiphenvl ethers, for example 2,2'-thiobis (6-tert-butyl-4-methylphenol), 2,2'-thiobis (4-octylphenol), 4,4'-thiobis (6-tert-butyl-3-methylphenol), 4, 4'-thiobis- (6-tert- butyl-2-methylphenol), 4,4'-thiobis (3, 6-di-sec-amylphenol) or 4,4'-bis (2, 6-dimethyl-4-hy- droxyphenyl) disulfide 1 6 Alkylidenebisphenols, for example 2, 2'-methylenebis (6-tert-butyl-4-methylphenol), 2,2'- methylenebis (6-tert-butyl-4-ethylphenol), 2, 2'-methylenebis (4-methyl-6- (a-methylcyclo- hexyl)-phenol), 2, 2'-methylenebis (4-methyl-6-cyclohexylphenol), 2, 2'-methylenebis (6- nonyl-4-methylphenol), 2, 2'-methylenebis (4, 6-di-tert-butylphenol), 2, 2'-ethylidenebis (4,6- di-tert-butylphenol), 2, 2'-ethylidenebis (6-tert-butyl-4-isobutyl phenol), 2, 2'-methylenebis (6- (a-methylbenzyl)-4-nonylphenol), 2, 2'-methylene-bis (6- (a, a-dimethylbenzyl)-4-nonylphe- nol), 4, 4'-methylenebis (2, 6-di-tert-butyl phenol), 4, 4'-methylenebis (6-tert-butyl-2-methyl- phenol), 1,1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 2,6-bis (3-tert-butyl-5-

methyl-2-hydroxybenzyl)-4-methylphenol, 1,1, 3-tris (5-tert-butyl-4-hydroxy-2-methyl- phenyl) butane, 1,1-bis (5-tert-butyl4-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobu - tane, ethylene glycol bis (3,3-bis (3'-tert-butyl4'-hydroxyphenyl) butyrate), bis (3-tert-butyl- 4-hydroxy-5-methylphenyl) dicyclo-pentadiene, bis (2- (3'-tert-butyl-2-hydroxy-5'-methyl- benzyl)-6-tert-butyl-4-methylphen yl) terephthalate, 1,1-bis (3, 5-dimethyl-2-hydroxy- phenyl) butane, 2,2-bis (3, 5-di-tert-butyl-4-hydroxyphenyl) propane, 2,2-bis (5-tert-butyl-4- hydroxy-2-methylphenyl)-4-n-dodecylmercaptobutane or 1,1, 5,5-tetra (5-tert-butyl-4-hy- droxy-2-methylphenyl)-pentane 1. 7 0-N-and S-benzyl compounds, for example 3,5, 3', 5'-tetra-tert-butyl-4, 4'-dihydroxydiben- zyl ether, octadecyl 4-hydroxy-3, 5-dimethylbenzylmercaptoacetate, tridecyl 4-hydroxy- 3, 5-di-tert-butylbenzylmercaptoacetate, tris (3, 5-di-tert-butyl) amine, bis (4-tert-butyl-3-hy- droxy-2, 6-dimethylbenzyl) dithioterephthalate, bis (3, 5-di-tert-butyl-4-hydroxybenzyl) sul- fide or isooctyl 3, 5-di-tert-butyl-4-hydroxy-benzylmercaptoacetate 1.8 Hvdroxybenzvlated malonates, for example-dioctadecyl 2,2-bis (3, 5-di-tert-butyl-2- hydroxybenzyl) malonate, dioctadecyl 2- (3-tert-butyl-4-hydroxy-5-methylbenzyl)-malonate, d-dodecyl mercaptoethyl-2, 2-bis (3, 5-di-tert-butyl-4-hydroxybenzyl)-malonate or di (4- (1,1, 3, 3-tetramethylbutyl) phenyl) 2, 2-bis (3, 5-di-tert-butyl-4-hydroxybenzyl) malonate 1. 9 Aromatic hydroxybenzyl compounds, for example 1,3, 5-tris (3, 5-di-tert-butyl-4- hydroxybenzyl)-2, 4, 6-trimethyl benzene, 1,4-bis (3, 5-di-tert-butyl-4-hydroxybenzyl)-2, 3,5, 6- tetramethyl benzene or 2, 4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) phenol 1.10 Triazine compounds, for example 2, 4-bisoctylmercapto-6- (3, 5-di-tert-butyl-4- hydroxyanilino)-1, 3,5-triazine, 2-octylmercapto-4, 6-bis (3, 5-di-tert-butyl-4-hydroxyanilino)- 1,3, 5-triazine, 2-octylmercapto-4, 6-bis (3, 5-di-tert-butyl-4-hydroxyphenoxy)-1, 3,5-triazine, 2,4, 6-tris (3, 5-di-tert-butyl-4-hydroxyphenoxy)-1, 2, 3-triazine, 1,3, 5-tris (3, 5-di-tert-butyl-4- hydroxybenzyl)-isocyanurate, 1,3, 5-tris (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) iso- cyanurate, 2,4, 6-tris (3, 5-di-tert-butyl-4-hydroxyphenylethyl)-1, 3,5-triazine, 1,3, 5-tris (3,5- di-tert-butyl-4-hydroxyphenylpropionyl) hexahydro-1,3, 5-triazine or 1,3, 5-tris (3, 5-dicyclo- hexyl-4-hydroxybenzyl)-isocyanurate 1.11 Benzylphosphonates, for example dimethyl 2, 5-di-tert-butyl-4-hydroxybenzyl- phosphonate, diethyl 3, 5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl 3,5-di- tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl 5-tert-butyl-4-hydroxy-3-methylben- zylphosphonate or the calcium salt of the monoethyl ester of 3, 5-di-tert-butyl-4-hydroxy- benzylphosphonic acid

1.12 Acylaminophenols, for example 4-hydroxylauranilide, 4-hydroxystearanilide or octyl N- (3, 5-di-tert-butyl-4-hydroxyphenyl) carbamate 1.13 Esters of ß-(3 5-di-tert-butvi-4-hydroxyphenyl) propionic acid, ß-(5-tert-butyl-4-hydroxy- 3-methylphenyl) propionic acid, P- (3, 5-dicyclohexyl-4-hydroxyphenyl)-propionic acid, 3,5- di-tert-butyl-4-hydroxyphenylacetic acid or D-(5-tert-butyl-4-hydroxyphenyl)-3-thiabutyric acid with mono-or polyhydric alcohols, e. g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1, 6-hexanediol, 1, 9-nonanediol, ethylene glycol, 1, 2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxalamide, 3-thiaundecanol, 3- thiapentadecanol, trimethyl-hexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha- 2,6, 7-trioxabicyclo (2. 2. 2) octane, glycerol or transesterification products based on natural triglycerides of, for example, coconut oil, rape seed oil, sunflower oil or colza oil 1.14 Amides of a- (3, 5-di-tert-butvl-4-hydroxyphenyl) propionio acid, e. g. N, N'-bis (3,5-di-tert- butyl-4-hydroxyphenylpropionyl) hexamethylenediamine, N, N'-bis (3, 5-di-tert-butyl-4-hy- droxyphenylpropionyl) trimethylenediamine or N, N'-bis (3, 5-di-tert-butyl-4-hydroxyphenyl- propionyl) hydrazine 1. 15 Ascorbic acid (vitamin C) 1.16 Amine-type antioxidants, for example N, N'-diisopropyl-p-phenylenediamine, N, N'-di- sec-butyl-p-phenylenediamine, N, N'-bis (1, 4-dimethylpentyl)-p-phenylenediamine, N, N'- bis (1-ethyl-3-methyl-pentyl)-p-phenylenediamine, N, N'-bis (1-methyl-heptyl)-p-phenylen- diamine, N, N'-dicyclohexyl-p-phenylenediamine, N, N'-diphenyl-p-phenylenediamine, N, N'-di-(naphth-2-yl)-p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N- (1, 3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, N-(1-methylheptyl)-N'-phenyl-p- phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine, 4-(p-toluenesulfona- mido) diphenylamine, N, N'-dimethyl-N, N'-di-sec-butyl-p-phenylenediamine, diphenyl- amine, N-allyidiphenylamine, 4-isopropoxy-diphenylamine, N-phenyl-1-naphthylamine, N- (4-tert-octylphenyl)-1-naphthylamine, N-phenyl-2-naphthylamine, octylated diphenyl- amine, e. g. p, p'-di-tert-octyidiphenyl-amine, 4-n-butylaminophenol, 4-butyrylamino-phe- nol, 4-nonanoylamino-phenol, 4-dodecanoylaminophenol, 4-octadecanoylamino-phenol, di- (4-methoxyphenyl)-amine, 2, 6-di-tert-butyl-4-dimethylamino-methyl-phenol, 2, 4'-dia- mino-diphenylmethane, 4, 4'-diamino-diphenylmethane, N, N, N', N'-tetramethyl-4, 4'-dia- mino-diphenylmethane, 1, 2-di-((2-methyl-phenyl)-amino)-ethane, 1, 2-di- (phenyl- amino) propane, (o-tolyl) biguanide, di (4- (l', 3'-dimethyl-butyl)-phenyl) amine, tert-octylated N-phenyl-1-naphthylamine, a mixture of mono-and dialkylated tert-butyl/tert-octyidi- phenylamines, a mixture of mono-and dialkylated nonyidiphenylamines, a mixture of

mono-and dialkylated dodecyldiphenylamines, a mixture of mono-and dialkylated iso- propyl/isohexyldiphenylamines, mixtures of mono-and dialkylated tert-butyidiphenyl- amines, 2, 3-dihydro-3, 3-dimethyl-4H-1, 4-benzothiazine, phenothiazine, a mixture of mono-and dialkylated tert-butyl/tert-octyl-phenothiazines, a mixture of mono-and dialky- lated tert-octyl-phenothiazines, N-allylphenothiazine, N, N, N', N'-tetraphenyl-1, 4-diamino- but-2-ene, N, N-bis- (2, 2,6, 6-tetramethylpiperidin-4-yl) hexamethylenediamine, bis- (2, 2, 6, 6- tetramethylpiperidin-4-yl) sebacate, 2,2, 6, 6-tetramethylpiperidin-4-one or 2,2, 6,6- tetramethylpiperidin-4-ol and 1.17 Aliphatic or aromatic phosphites, esters of thiodipropionic acid or of thiodiacetic acid, or salts of dithiocarbamic or dithiophosphoric acid, 2,2, 12, 12-tetramethyl-5, 9-dihydroxy- 3,7, 1-trithiatridecane or 2, 2,15, 15-tetramethyl-5, 12-dihydroxy-3,7, 10,14-tetrathiahexa- decane; 2 Examples of metal passivators, for example for copper, are: 2. 1 Benzotriazoles and their derivatives, for example 4-or 5-alkylbenzotriazoles (e. g. tolutria- zole) and derivatives thereof, 4,5, 6, 7-tetrahydrobenzotriazole, 5, 5'-methylenebisbenzotri- azole ; Mannich bases of benzotriazole or tolutriazole, such as 1- (di (2-ethyl- hexyl) aminomethyl) tolutriazole and 1-(di (2-ethylhexyl) aminomethyl)-benzotriazole ; alkoxyalkylbenzotriazoles, such as 1- (nonyloxymethyl)-benzotriazole, 1- (1-butoxyethyl)- benzotriazole and 1- (1-cyclohexyloxybutyl)-tolutriazole 2. 2 1, 2, 4-Triazoles and derivatives thereof, for example 3-alkyl (or aryl)-1, 2, 4-triazoles, Man- nich bases of 1,2, 4-triazoles such as 1- (di (2-ethylhexyl) aminomethyl)-1, 2, 4-triazole ; alkoxyalkyl-1, 2, 4-triazoles such as 1-(1-butoxyethyl)-1, 2, 4-triazole ; acylated 3-amino- 1,2, 4-triazoles 2.3 Imidazole derivatives, for example 4, 4'-methylenebis (2-undecyl-5-methyl-imidazole), bis ( (N-methyl) imidazol-2-yl) carbinol octyl ether 2. 4 Sulfur-containina heterocyclic compounds, for example 2-mercaptobenzothiazole, 2,5- dimercapto-1,3, 4-thiadiazole, 2, 5-dimercaptobenzothiadiazole and derivatives thereof ; 3,5-bis (di (2-ethylhexyl) aminomethyl)-1, 3, 4-thiadiazolin-2-one and 2. 5 Amino compounds, for example salicylidenepropylenediamine, salicylaminoguanidine and salts thereof ; 3 Examples of rust inhibitors are: 3. 1 Organic acids, their esters, metal salts, amine salts and anhydrides, for example alkyl- and alkenylsuccinic acids and the partial esters thereof with alcohols, diols or hydroxy-

carboxylic acids, partial amides of alkyl-and alkenylsuccinic acids, 4-nonylphenoxyacetic acid, alkoxy-and alkoxyethoxycarboxylic acids, such as dodecyloxyacetic acid, dodecy- loxy (ethoxy) acetic acid and the amine salts thereof, and also N-oleoylsarcosine, sorbitan monooleate, lead naphthenate, alkenylsuccinic anhydrides, for example dodecenylsuc- cinic anhydride, 2- (2-carboxyethyl)-1-dodecyl-3-methylglycerine and its salts, especially sodium and triethanolamine salts 3. 2 Nitrogen-containing compounds, for example : 3.2. 1 Primary, secondary or tertiary aliphatic or cycloaliphatic amines and amine salts of or- ganic and inorganic acids, for example oil-soluble alkylammonium carboxylates, and also 1- (N, N-bis (2-hydroxyethyl) amino)-3- (4-nonylphenoxy) propan-2-ol 3.2. 2 Heterocyclic compounds, for example : substituted imidazolines and oxazolines, 2- heptadecenyl-1- (2-hydroxyethyl)-imidazoline 3. 3 Phosphorus-containing compounds, for example Amine salts of phosphoric acid partial esters or phosphonic acid partial esters, zinc dialkyldithiophosphates 3. 4 Sulfur-containinq compounds, for example: barium dinonyinaphthalene-sulfonates, cal- cium petroleumsulfonates, alkylthio-substituted aliphatic carboxylic acids, esters of ali- phatic 2-sulfocarboxylic acids and salts thereof and 3. 5 Glycerol derivatives, for example: glycerol monooleate, 1- (alkylphenoxy)-3- (2-hy- droxyethyl) glycerines, 1-(alkylphenoxy)-3-(2, 3-dihydroxypropyl) glycerines, 2-carboxyal- kyl-1, 3-dialkylglycerines ; 4 Examples of viscosity index improvers are: Polyacrylates, polymethacrylates, vinylpyrrolidone/methacrylate copolymers, polyvinylpyr- rolidones, polybutenes, olefin copolymers, styrene/acrylate copolymers, polyethers ; 5 Examples of pour point depressants are: Polymethacrylate, alkylated naphthalene derivatives; 6 Examples of dispersants/surfactants are: Polybutenylsuccinamides or-imides, polybutenylphosphonic acid derivatives, and basic magnesium, calcium and barium sulfonates, phenolate and salicylates ; 7 Examples of antifoams are: Silicone oils and polymethocrylen ; 8 Examples of demulsifiers are:

Polyetherpolyols and dinonylnaphthalenesulfonates ; 9 Examples of friction modifiers are: Fatty acids and their derivatives (i. e. natural esters of fatty acids such as glycerol monooleate), amides, imides and amines (i. e. oleylamine), sulfur containing organo- molybdenum dithiocarbamates, sulfur-phosphorus containing organomolybdenum dithio- phosphates, sulfur-nitrogen containing organomolybdenum compounds based on dis- persants, molybdenum carboxylate salts, molybdenum-amine complexes, molybdenum amine/alcohol/amid complexes and molybdenum cluster compounds, Teflon and mo- lybdenum disulfide ; 10 Examples of additional antiwear additives are: 10.1 Sulfur-and/or phosphorus-and/or halogen-containing compounds, such as sulfurized olefins and vegetable oils, zinc dialkyldithiophosphates, tritolyl phosphate, tricresyl phos- phate, chlorinated paraffins, alkyl and aryl di-and trisulfides, amine salts of mono-and dialkyl phosphates, amine salts of methylphosphonic acid, diethanolaminomethyltolyltria- zole, di- (2-ethylhexyl)-aminomethyltolyltriazole, derivatives of 2, 5-dimercapto-1, 3,4- thiadiazole, ethyl (bisisopropyloxyphosphinothioyl) thiopropionate, triphenyl thiophosphate (triphenyl phosphorothioate), tris (alkylphenyl) phosphorothioates and mixtures thereof (for example tris (isononylphenyl) phosphorothioate), diphenylmonononylphenyl phos- phorothioate, isobutylphenyl diphenyl phosphorothioate, the dodecylamine salt of 3-hy- droxy-1, 3-thiaphosphetan 3-oxide, trithiophosphoric acid 5,5, 5-tris-isooctyl 2-acetate, de- rivatives of 2-mercaptobenzothiazole, such as 1-N, N-bis (2-ethylhexyl) aminomethyl-2- mercapto-1H-1, 3-benzothiazole, and ethoxycarbonyl 5-octyidithiocarbamate 10.2 Dihydrocarbyl dithiophosphate metal salts, where the metal is aluminum, lead, tin manganese, cobalt, nickel, zinc or copper, but most often zinc. The zinc salt (zinc dialkyl dithiophosphate) is represented as where R and R'are independently Cri-620 alkyl, C3-C20 alkenyl, C5-C12 cycloalkyl, C7- C13 aralkyl or C6-Cio aryl, for example R and R'are independently Cl-Cl2 alkyl

10.3 Antiwear additives as described in U. S. Patent Nos. 4,584, 021 ; 5, 798, 321 ; 5,750, 478 ; 5, 801, 130 ; 4, 191, 666; 4,720, 288; 4,025, 288 ; 4,025, 583 and WO 095/20592, which U. S. patents are incorporated herein by reference; amines for example polyalkylene amines such as ethylene diamine, diethylene triamine, triethylene tetraamine, tetraethylene pen- tamine, pentaethylene hexamine, nonaethylene decamine and aryl amines as described in U. S. Patent No. 4,267, 063, herein incorporated by reference; salts of amine phos- phates comprising specialty amines and mixed mono-and di-acid phosphates ; the mono- and di-acid phosphate amines have the structural formulae:

wherein R27 is hydrogen, Cl-C25 linear or branched chain alkyl which is unsubstituted or substituted by one or more C-C6alkoxy groups, a saturated acyclic or alicyclic group, or aryl ; R28 is Ci-C25 linear or branched chain alkyl which is unsubstituted or substituted by one or more Ci-C6alkoxy groups, a saturated acyclic or alicyclic group, or aryl ; R29 is hydrogen, Cl-C2, 5 linear or branched chain alkyl, a saturated or unsaturated acyclic or alicyclic group, or aryl ; and are hydrogen or Cl-Cl2 linear or branched chain alkyl ; and R30 and R31 are, each independently of the other, Cl-C25 linear or branched chain alkyl, a saturated or unsaturated acyclic or alicyclic group, or aryl. Preferably, R27 and R28 are lin- ear or branched Cl-C12 alkyl ; and R29, Rso and R31 are linear or branched Ci-Cis alkyl ; According to a preferred embodiment Irgalube@3 349 (Ciba Specialty Chemicals) has been found to be very useful, particularly by enhancing the wear performance of the base oil such that it meets stringent military performance specifications; IRGALUBE 349 has the formula wherein R33 is n-hexyl, R34 is C11-C14 branched alkyl, and when x=1 then y=2 ; when x=2 then y=1 ; IRGALUBE349 is a mixture of amine phosphates, CAS # 80939-62-4 10.4 Other conventional antiwear additives are compounds of the formula

in which R, and R2 independently of one another are C3-C18 alkyl, C5-C, 2 cycloalkyl, C5- C6 cycloalkylmethyl, C>-C10 bicycloalkylmethyl, Cg-Co tricycloalkylmethyl, phenyl or C7- C24 alkylphenyl or together are (CH3) 2C (CH2) 2, R3 is hydrogen or methyl. According to a preferred embodiment, IRGALUBE 353, a dialkyl dithiophosphate ester, CAS # 268567-32-4, is used.

The present fuel compositions can contain, in addition to the borate and boronate additives, other additives which are well known to those of skill in the art. These include antiknock agents such as tetralkyl lead compounds, lead scavengers such as haloalkanes (e. g., ethyl- ene dichloride and ethylene dibvromide), deposit preventers or modifiers such as triaryl phosphates, dyes, cetane improvers, antioxidants such as 2, 6-di-tert-butyl-4-methylphenol, rust inhibitors such as alkylated succinic acids and anhydrides, bacteriostatic agents, gum inhibitors, metal deactivators, demulsifiers, upper cylinder lubricants and anti-icing agents.

The present borates and boronates can be introduced into the lubricating oil in manners known per se. The compounds are readily soluble in oils. They may be added directly to the lubricating oil or they can be diluted with a substantially inert, normally liquid organic diluent such as naphtha, benzene, toluene, xylene or a normally liquid oil or fuel to form an additive concentrate or master batch. These concentrates generally contain from about 10% to about 90% by weight additive and may contain one or more other additional additives. The present borates and boronates may be introduced as part of an additive package.

The present invention is further illustrated by the following Examples: Example 1 Di-n-dodec-1-yl-2-(pyrid-2-yl) ethyl borate A 500 mi glass reaction vessel equipped with a magnetic stir bar and Dean-Stark tube fitted with a reflux condenser is charged with 12.3 g of 2- (2-hydroxyethyl) pyridine, 37.2 g of 1-do- decanol, 6.2 g of boric acid and 250 mi of toluene. The mixture is stirred and heated at reflux for 5 h, during which time ca. 5 ml of water is removed, indicating ester formation. The solu- tion is filtered to remove haziness, the solvent is removed by vacuum distillation, and the bo- rate ester is obtained as a clear pale-yellow oil.

Example 2

n-Octadec-1-yl-2-(pyrid-2-yl) ethyl phenylboronate A 200 ml glass reaction vessel equipped with a magnetic stir bar and Dean-Stark tube fitted with a reflux condenser is charged with 5.69 ml of 2- (2-hydroxyethyl) pyridine, 13.7 g of 1- octadecanol, 6.29 g of phenylboronic acid, and 150 ml of toluene. The mixture is stirred and heated at reflux for 16 h, during which time 1.8 mi of water is removed, indicating ester for- mation. The solution is filtered to remove haziness and the solvent removed by vacuum dis- tillation, resulting in 23.4 g of a pale yellow oil which solidifies to a waxy substance on cool- ing.

Example 3 n-Oct-1-yl- (pyrid-2-yl) ethyl phenylboronate A 200 mi glass reaction vessel equipped with a magnetic stir bar and Dean-Stark tube fitted with a reflux condenser is charged with 5. 69 ml of 2- (2-hydroxyethyl) pyridine, 7.96 g of 1- octanol, 6.29 g of phenylboronic acid, and 150 mi of toluene. The mixture is stirred and heated at reflux for 16 h, during which time 1.8 ml of water is removed, indicating ester for- mation. The solution is filtered to remove haziness and the solvent removed by vacuum dis- tillation, resulting in 16 g of a viscous dark yellow oil.

Example 4 n-Ole-1-yl-2-(pyrid-2-yl) ethyl phenylboronate A 200 mi glass reaction vessel equipped with a magnetic stir bar and Dean-Stark tube fitted with a reflux condenser is charged with 5. 69 ml of 2- (2-hydroxyethyl) pyridine, 18.6 mi of oleyl alcohol, 6.29 g of phenylboronic acid, and 150 mi of toluene. The mixture is stirred and heated at reflux for 16 h, during which time 1.8 mi of water is removed, indicating ester for- mation. The solvent is removed by vacuum distillation, resulting in 24 g of a viscous dark yellow oil.

Example 5 Di-n-oct-1-yl-2-(pyrid-2-yl) ethyl borate A 2000 ml glass reaction vessel equipped with a magnetic stir bar and Dean-Stark tube fitted with a reflux condenser is charged with 75.0 g of 2- (2-hydroxyethyl) pyridine, 158.7 g of 1- octanol, 61.8 g of boric acid and 1500 mi of toluene. The mixture is stirred and heated at re- flux for 18 h, during which time ca. 33 mi of water is removed, indicating ester formation. The solution is filtered to remove haziness, the solvent is removed by vacuum distillation, and the resulting oil is filtered through a glass frit to give the borate ester as a clear pale-yellow oil.

Example 6 Antiwear properties Antiwear properties are measured on a PCS Instruments Mini-Traction Machine, modified with a Pin-on-Disc attachment, in which a stationary pin (500 x 500 Il) is held against a ro- tating disc, with a fixed load applied at a constant temperature. Wear is measured as the dis- placement of the pin, due to loss of material from the pin. The test oil is a zero S, very low P automotive engine oil,-fully formulated except that no antiwear additive is included. The reac- tion test conditions are 10N load, oil temperature 100°C. Wear data is recorded for 60 min, and the average wear rate is reported here as the linear regression slope of the wear curve.

Additives are reported in weight percent based on the formulated oil. Oil Wear Rate Control (no antiwear additive) 279) /h + 1. 2% ZDDP 03. 0 Sh +1% compound of Ex. 9 ZDDP is zinc dialkyl dithiophosphate = a'secondaryZDDP at 1. 2% provides 0. 1% P.

Example-7 Four Bell antiwear testing Antiwear properties of the borate esters of the present invention are tested at a level of 1. 0 wt% in a test oil. The test oil is a P-free, very low S automotive engine oil, fully formulated except that no antiwear additive is included in the formulation. The antiwear, properties are determined in the Four-Ball Wear Test under ASTM D 1472 test conditions, using a 40 kg (392 N) load. The test is run in duplicate, and the test results, Average Wear Scar Diameter (mm) are reported. The numerical value of the test results decreases with an increase of ef- fectiveness of the additive. Test Compound Wear Scar Diameter Test oil (no antiwear additive) 0.675 Test Oil (1% Compound Example 1) 0.65 Test Oil (1% Compound Example 5) 0.615 Test Oil (1% Zn DDP) 0.61