CA1257606A - Boron-containing heterocycles and lubricating compositions - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE

A boxon-containing heterocyclic compound prepared by reacting a primary amine or ammonia with an alkylene oxide or epoxide and then reacting concurrently or subsequently this reaction intermediate with a boric acid. This boron-containing heterocyclic compound may further be reacted with a metal, metaloid or other metal compound and even further contain sulfur, such as a sulfide group.
The boron-containing heterocyclic compound provides extreme pressure anti-wear properties when provided in a lubricating composition. The lubricating composition may also comprise anti-oxidants, copper corrosion inhibitors, and lead corrosion inhibitors.
The anti-wear properties of a lubricating composition can be enhanced using the borates of the present inven-tion in conjunction with a copper compound.

Description

This invention relates to lubricating oils and more particularly to improved lubricating oils containing additives, such as anti-wear and friction-reducing com-pounds, corrosion inhibitors and oxidation inhibitors.
It is well recognized in the petroleum industry that boron-containlny compounds are desirable additives for for lubricating oils. One such boron con-taining compound is disclosed in United States Patent 3,224,971 to Knowles et al. which relates to intracomplexed borate esters and to lubricating compositions containing said esters. The borate esters are organo-boron compounds derived from boric acid and a bis(o-hydroxy-alkylphenyl) amine or sulfide.
Another extreme pressure lubrication composition is disclosed in U.S. Patent 3,185,644 to Knowles et al , which relates to lubricating compositions containing amine salts of boron-containing compounds. The amine salts are formed by reaction of a hydroxy substituted amine and a trihydrocarbyl borate. The amine-borate compounds thus formed are described as useful as load carrying additives for mineral and synthetic base lubricating oils.
Boric-acid-alkylolamine reaction products and lubricating oils containing the same are disclosed in United States Patent 3,227,739 to Versteeg. These amine type products are prepared by reacting equal molar propor-tions of diethanolamine or dipropanolamine and a long chain, 1, 2-epoxide. The intermediate reaction product thus produced is reacted with boric acid to produce the final reaction product. These compounds are added to lubricants to prevent rust formation.

Another boron ester composition is described in United ~tates Patent 3,269,853 to English et al. which discloses a boron ester curing agent which consists of a cyclic ring structure containing boron, oxygen, nitrogen, carbon and hydrogen.
Another boron composition is disclosed in United States Patent 3,598,855 to Cyba which relates to cyclic borates of polymeric alkanolamines Eormed by reacting a borylating agent with a polymeric alkanolamine. The com-pounds thus formed are described as additives for a widevariety of petroleum products including lubricating oils.
Currently, there are phosphorus-containing additives which provide extreme pressuxe, anti-wear and/or friction-reducing properties to automotive engine oils.
However, with the advent of the catalytic converter, alternative additives are needed. During combustion in an automotive engine, any oil which leaks or seeps into the combustion chamber yields phosphorus deposits which poison the catalyst in the catalytic converter. ~s a result, there is a need for automotive engine oil additives which are phosphorus-free but provide useful extreme pressure, anti-wear, and/or friction-reducing properties to the oil.
Briefly, the invention resides in a boron-containing heterocyclic compound of the formula:

[R - \R2 ~ ~r~

wherein M is an inorganic or organic radical; R, Rl and R2 are the same or different organic radical; and y is an integer.
The invention further resides in a boron-containing heterocyclic compound of the foxmula:
r /Rl O~

Y
wherein y is an integer; M is a metal selected from the periodic groups IB, IIB, IIIB, IVB, V~3, VIB, VIIB, VIII, IIIA, IVA, VA; R is, an inorganic radical or a Cl to C50 organic radical; and Rl and R2 are the same or di~ferent Cl to C50 organic radical.
The invention further resides in a boron-contain-ing heterocylic compound of the formula:

- ~1 - -R N~ ~B M~Y

2 i y wherein y is an integer; M is a Cl to C50 organic radical;
R is an inorganic radical or Cl to C50 organic radical;
and Rl and R2 are the same or different C3 or greater substituted or unsubstituted organic radicals provided that at least one of Rl and R2 is other than an unsub-stituted or alkyl-substituted ortho-alkyl phenyl bridge with the o~cygen connected to the phenyl carbon.
The invention further resides in a boron-containing heterocyclic compound of the formula:

~7~

[ R - ~N < R~ O B- -O ]

wherein M is hydrogen; R is an inorganic radical or a C1 to C50 orc~anic radical; and R1 and R2 are the same or different C4 or greater substituted or unsubstituted organic radicals provided at least one of R1 or R2 is other than an unsubstituted or alkyl-substituted ortho-alkyl phenyl bridye with the oxygen connected to the phenyl carbon.
The invention additionally resides in an extreme pressure, anti-wear and friction-reducing lubricating oil and a minor amount of a boron~containing, heterocyclic compound as above-described.
The boron-containing, heterocyclic compounds may conveniently be prepared by reacting either a saturated or unsaturated primary amine wi-th an organic epoxide, such as an alkyl epoxide or an aromatic epoxide, to form a reaction product. The reaction product thus formed is reacted with boric acid to form a boron-containing, heterocyclic com-pound. Next, the boron-containiny, heterocyclic compound may be reacted with either a salt of a metal, metalloid, or semi-metal to produce a metal derivative of the boron-containing, heterocyclic compound or with an alcohol to produce an ester-type derivative.
Alternatively, the boron-containing heterocyclic compounds may be produced by reacting either sulfur and/or a halogen and/or a sulfur halide with a horon-containing, heterocyclic compound containing unsaturateds in the R, R1, R2, and M radicals.

The above-described, boron-containing, hetero-cyclic compounds impart extreme pressure, anti-wear and friction-reducing properties to lubricating oils when added to said oils at use concentrations.
Another embodiment of the invention resides in a lubricatlng composition comprising a boron-containing, heterocyclic compound of the invention, and optionally any of (1) a polysulfide derivative of 2,5-dimercapto-1,3,~-thiodiazole, (2) terephthalic acid, and 13) either a bis(dithiobenzil) metal derivative, a sulfur bridged, bis(hindered phenol) or an alkylated or dialkylated diphenyl amine or a mixture thereof.
In still another embodiment of the invention, a copper compound is used with a borate of the present invention in a lubricating compound. The copper compound enhances the anti-wear properties of such a composition.
The present invention resides in extreme pressure, anti-wear and friction-reducing lubricating oil compositions comprising a major amount of an oil of lubricating viscosity and a minor amount of a boron-containing, heterocyclic com-pound~ Alternatively, corrosion inhibitors and anti-oxidants may be incorporated into the lubricating composition.
Anti-wear, friction-reducing and extreme pressure (or "E.P.") additives, as they are commonly called, are chemicals which are added to lubricating compositions to reduce friction and reduce or prevent destructive metal-to-metal contact in the lubrication of moving surfaces.

It has now been discovered -that certain novel oil-soluble or dispersible boron-containing, heterocyclic compounds, when added to lubricatiny oils or grease, not only improve the ability of the lubricant to prevent seizure of the parts being lubricated (i.e., good E.P.
properties) but in addition greatly reduce the amount of friction and wear of such moving parts.
The boron-containlng, heterocyclic compounds described herein may be incorporated in a wide variety of lubricating oils, for example, mineral oil, crude oil, synthetic oil, industrial lubricating oils, cutting oil, metal working fluids and grease. Ano-ther use for the additive of the invention is in those fuels, e.g., certain aviation fuels and the like, wherein lubrication properties are desired. ~lowever, the most preferred use for the lubri-cating additive of the invention is in automotive engine oils. In this application, the boron-containing additives provide extreme pressure, anti-wear, and friction-reducing properties to the oil, and, upon combustion, prove innocu-ous to the conventional catalytic converter in modernautomobiles.
If desired, the boron-containing, heterocyclic compounds described herein may be employed in conjunction with other additives commonly used in petroleum products.
Thus, there may be added to the oil compositions of this invention rust and corrosion inhibitors, emulsifying agents, antioxidants or oxidation inhibitors, dyes, haze inhibitors, anti-static agents, detergents, dispersants, viscosity index improvement agents, pour point reducing ~X~

agents, and other extreme pressure and anti-wear additives, such as the zinc dithiophosphate, txiphenyl phosphorothio-nate, etc. Soaps or other thickening agents may be added to the lubricating oil compositions to form compositions having the consistency of a grease. When other additives are employecl, it may be desirable, although not necessary, to prepare additive concentrates comprising concentrated solutions of the herein boron-containing, heterocyclic compounds together with said other additives whereby the several additives are added simultaneously. Dissolution of the additive or additive concentrate into the oil composition may be facilitated by mixing accompanied with mild heating, but this is not absolutely essential.
The herein-described boron-containing, hetero-cyclic compounds may be incorporated in the lubricating oils in any convenient way. Thus, boron-containing, heterocyclic compounds may be added directly to the oil by dissolving the desired boron derivative in the lubricating oil at the desired level of concentration.
Normally, the boron-containing, heterocyclic compound is blended with the lubricating oil such that its concentration is from about 0.1 to about 15 percent by weight, preferably from about 0.5 to about 10 percent by weight of the resultant oil composition. Alternatively, the compounds may first be blended with suitable solvents to form concentrates that may readily be dissolved in the appropriate oil at the desired concentration. If a concentrate is prepared, it is presently preferred that such concentrate comprise about 75 percent by weight of 6~3~

the compound, with the balance being a solvent. Sultable solvents which may be used for this purpose are naphtha, light mineral oil (iOe., 150 neutral -to ~50 neutral) and mixtures thereof. The particular solvent selected should, of course, be selected so as not to adversely affect the other desired properties of the ultimate oil composition.
The boron-containiny, heterocyclic compounds of the present invention are represented generically by the following formula (I):

(I) R2 M Y
y In the foregoing formula, R is an inorganic radical, e.g., hydrogen, chlorine, bromine, etc., or an organic radical having rom about 1 to about 50 carbon atoms, typically about l to 30 carbon atvms, and preferably from about 1 to about 20 carbon atoms. Preferablyl R is derived from ali-phatic, alicyclic, or aromatic compounds. Most preferably, R is a substituted or unsubstituted hydrocarbyl group, particularly an alkyl, alkenyl, alkynyl, aryl, alkyLaryl or arylalkyl radical having from about 1 to about 30 carbon atoms, preferably from about 1 to about 20 carbon atoms, especially from about 9 to about 20 carbon atoms.
Rl and R2 are the same or different organic radicals bridging the nitrogen and oxygen atoms and have from about 1 to about 50 carbon atoms and preferably from about 2 to about 30 carbon atoms, with R1 and R2 oftentimes containing at least 3 or at least ~ carbon atoms. R1 and R2 are --8~

typically derived from aliphatic, alicyclic, or aromatic compounds and generally include at least two carbon atoms bridged between the nitrogen and oxygen atoms. Usually, Rl and R2 are the same or different substituted or unsub stituted hydrocarbyl or hyclrocarbylo~y groups. Typical hydrocarbyl groups, which Rl and R2 may be, are substituted or unsubstituted al~ylaryl, aryl, arylalkyl, alkyl, alkynyl, and alkenyl groups, with the most preferred radical bridging the oxygen and nitrogen atoms (in this and all embodiments hereinafter discussed with the exception of the embodiment typified by formula (IV) hereinafter) being an alkylaryl group wherein an ethylene radical bridges the oxygen and nitrogen atoms and an unsubstituted phenyl radical is bonded to the carbon closest to the oxygen atom, i.e., - N CH ~ CH - ~ - B -Typical hydrocarbyloxy groups which may bridge the nitrogen and oxygen atoms are those discussed hereinafter with respect to formula (IV). y is an integer from 1 to 4 and M is an organic or inorganic radical, but is usually either hydrogen or a metal, typically selected from the Groups IB, IIB, IIIB, IVB, VB, VIB, VIIB, VIII, IIIA, IVA, and VA of the Periodic Table, as found in the 1'Handbook of Chemistry and Physics," CRC Publishing Co., 46th Edition.
Preferably, M is hydrogen or a transitlon metal having an atomic number from 21 to 30 or a Group IVA metal of the Periodic Table or mixtures thereof, and still more pref-erably copper. If M is an organic radical, it is typically of 1 to 50 carbon atoms and is derived from an aliphatic, alicyclic, or aromatic compound. Preferred radicals, when M is organic, are chosen from the group consisting o~ substituted and unsubstituted alkyl, alkynyl, alkenyl, aryl, arylalkyl, and alkylaryl ~roups of between 1 and 50 carbon atoms, with methyl and cyclohexyl radicals being among the most preferred groups. Also among the most preferred groups, if M is organic, are substituted and unsubstituted phenyl yroups, with substituted phenyl groups being particularly preferred.
The phenyl group may be substituted with, for example, an acetyl group, a methyl radical, or an O-CH3 group. One of the most preferred substituted phenyl groups is the hindered phenyl group wherein the phenyl group is substituted at the 2 and 6 carbon atom of the phenyl ring with an organic group having more than 3 carbon atoms, e.g., the 2 r 6-di-tert-butyl phenyl groups, such as ~-methyl-2,6-di-tert-butyl phenyl. Hindexed phenyl groups provide the compound with hydrolytic stability. It has also been unexpectedly found that non-hindered phenyl groups, whether substituted or unsubstituted, also provide the compound with hydrolytic stability.
(It should be noted herein that the terms "alkyl," "alkenyl," and "alkynyl" include cyclic species thereoF, as well as the straight and branched chain species thereof. Also, for purposes of this invention, an "organic radical" is one which contains at least one carbon atom whereas an "inorganic radical" contains none.
The term "inorganic radical," as used herein, is intended to include metals, semi-metals, and metalloids, as well as true inorganic radicals, e.g.l -Cl, -Br, ~ SO3, and The metals, semi-metals, an~ meta].loids may be bond~d ionically, covalently, or associatively.) In one embodiment of the invention, useful when M is either hydrogen or a metal, but particularly when M is hydrogen, R is hydrogen or a substituted or unsubsti-tuted hydrocarby.l. group and at least one of R1 and R2, if both are aromatic, is other than an unsubstituted or alkyl substituted ortho-alkyl phenyl bridge, with the oxygen bonded at the ortho position relative to the alkyl group.
Usually, if both R1 and R2 are aromatic, at least one contains no carbon atoms or three to five carbon atoms of the same aromatic ring in a chain of atoms bridging (or connecting) the oxygen atom to the nitrogen atom.
Generally in this embodiment, R contains at least 9 carbon atoms if aliphatic and at least 7 carbon atoms if aromatic; further, R in this embodiment, and sometimes also R1 and R2, are organic radicals other than hydroxyhydrocarbyl groups, and particularly other than alkanol groups. Further still, it is preferred that at least one of R1 and R2 in this embodlment and even more preferably both are radicals other than an amino or hydrocarbylamino group, and it is further preferred that R1 and R2 contain only carbon atoms bridging the nitrogen and oxygen atoms, with none of said bridging carbon atoms being a member of an aromatic ring.
In a pre~erred embodiment, boron-containing, heterocyclic compounds of the present invention are of the followi.ng formula (II):

--1 1. ~

r~

1 4 ~5 (II~ R - 2~/ I R \B----O ~l~y C - I O

In this formula, R3 is hydrogen or an organic radical having from about 1 to about 30 carbon atoms, preferably from about 1 to about 20 carbon atoms. Most preferably, R3 is hydrogen or a substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, alkylaryl or arylalkyl radical having from about 1 to about 30 carbon atoms, preferably from about 1 to about 20 earbon atoms. R4, R5, R6 and R7 axe the same or different ancl are either an inorganic radical such as hydrogen or an organic radical, such as suhstituted or unsubstituted hydrocarbyl radicals having from 1 to about 50 carbon atoms, preferably from about 1 to 30 carbon atoms, wherein at least one (and preferably 20 at least two) of the said R4, R5, R6 or R7 i9 an aryl, alkylaryl or arylalkyl radical having from about 6 to about 30 earhon atoms- R8, Rg, Rlo and Rll are the same or different radicals selected from hydrogen or organic radicals such as substituted or unsubstituted hydrocarbyl groups; typieally, R8, R9, Rlo ancl Rll are either hydrogen or an alkyl group having from about 1 to about 6 carbon atoms. Yl is an integer from 1 to 4, and Ml is an inorganic or organic radical, but is preferably selected from hydrogen or a metal, typically selected from a transition metal having an atomic number of 21 through 30 or a Group IVA metal. If M1 is an organic radical, it is typically of 1 to 50 carbon atoms and is derived from an aliphatic, alicyclic, or aromatic compound. Preferred radicals, when M is organic, are chosen from the group consisting of substituted and unsubstituted alkyl, alkynyl, alkenyl, aryl, arylalkyl, and alkylaryl groups o~ 1 to 50 carbon atoms, with methyl and cyclohexyl radicals being among the most preferred. ~lso among the most preferred groups, if M is organic, are substituted and unsubstituted phenyl groups, with substituted phenyl groups being particularly preferred. The phenyl group may be substituted with, for example, an acetyl group, a methyl radical, or an -O-CH3 group. One of the most preferred substituted phenyl groups is the hindered phenyl group wherein the phenyl group is substituted at the 2 and 6 carbon atom of the phenyl ring with an organic group having more than 3 carbon atoms, e.g., 2,6-di-tert-butyl phenyl groups, such as 4-methyl-2,6 di-tert-butyl phenyl. Hindered phenyl groups provide the compound with hydrolytic stability. It has also been unexpectedly found that non-hindered phenyl groups, whether substituted or unsubstituted, also provide the compound with hydrolytic stability.
In a preferred embodiment of the invention, R4, R7~ R8, Rg, Rlo and Rll in formula (II) are hydrogen or substituted or unsubstituted alkyl groups, with hydrogen being especially preferred for all six radicals, and R5 and R6 are aromatic radicals, preferably such as alkylaryl, arylalkyl, or aryl radicals, but most preferably are both unsubstituted phenyl radicals. This embodiment of the invention, i.e., the embodiment containing aromatic ~5~

radicals ~and particularly unsubstituted phenyl radicals), has the added advantage of enhanced hydrolytic stability and solubility in lubricating oils.
~ he ahove-described, boron containing, hetero-cyclic compounds are produced by (A) reacting a primary amine or ammonia with an alkylene oxide or epoxide or an aromatic oxide. The resulting product is then reacted with boric acid to give the corresponding boron~containing, heterocyclic compound. Primary amines useful in preparing the heterocyclic compounds of the present invention have the chemical formula RNH2 wherein R is an organic or inorganic radical, preferably where R contains I10 more than 30 carbon atoms. Amines which are suitable for use herein include saturated amines such as methylamine, ethylamine, propylamine, butylamine, octadecylamine, dodecylamine, cyclohexylamine, phenylamine, cocoamine, and unsaturated amines such as tallowamine and oleylamine and mixtures thereof. The organic radical associated with such amines (e.g., the methyl group of methylamine, the ethyl group of ethylamine, etc.) will ultimately be the R
group side chain emanating from the nitrogen atom o~ the heterocyclic borate of the invention. Thus, the R group side chain is determined by choice of amine, and if it is clesired tha-t R be inorganic rather than organic, then one may select ammonia to ensure that R is hydrogenl bromoamine to ensure that R is bromine, chloroamine to ensure that R
is chlorine, hydroxylamine -to ensure that R is an OH
group, etc. However, since it is preferred in all embodi ments of the invention that the R group side chain be organic in nature, the preferred amines for use in prepar-ing the he-terocyclic borates of the invention will be of formula RNH2, wherein R is an organic radical.
A wide variety of alkylene oxides or epoxides may be used to prepare the precursor for the heterocyclic compounds herein. Typical alkylene oxides or epoxides which are suitable for use include ethylene oxide, propylene oxide, 1,2-epoxy-butane, cyclohexene oxide, cyclooctene oxide, and cyclododecene oxide, and mixtures thereof.
Generally, the primary amine (or ammonia) is reacted with an alkylene oxide or epoxide, optionally in the presence of a solvent, for example toluene, to produce a dialkoxylated amine. The primary amine and alkene o~ide or epoxide are reacted at a molar ratio typically of about 1:2. If added~ the solvent is introduced in sufficient quantity to dissolve or disperse the reactants. After the reaction proceeds to completion, the solvent is removed from the reaction product, for example, by evaporation, distillation, etc.
Next, the dialkoxylated amine is reacted with boric acid at a typical molar ratio of about 1:1, option-ally in the presence of a solvent, for example, xylenes, benzene, toluene, etc~, to produce the heterocyclic compound required herein. If used, the solvent w~ll normally comprise from about 20 to about 50 weight percent, especially from about 30 to about 40 weight percent of the reaction mixture. The heterocyclic compound thus produced will contain from about 0.5 to about 10 weight percent, preferably from about 2 to about 5 weight percen-t of boron. The reactions herein are typically conducted under reflux at a temperature of from about 176 E'. (80 C.) to about 392 F. (200 C.), especially from about 176 F.
(80 C.) to about ~00 F. (14~.~9 C.), at atmospheric pressure for about 1 to about 5 hours.
It is also possible to prepare a suitable heterocyclic compound herein from an aromatic oxide (or aromatic epoxides). Aromatic oxides (or aromatic epoxides) suitable for use herein preferably are of the following formula (III):

(III) R12 ~ C - f Rl5 R13 ~14 wherein at least one of said R12, R13, Rl4 or Rl5 is aryl, alkylaryl or arylalkyl with the remaining R groups being independently hydrogen or an organic radical having 1 to 30 carbon atoms, preferably hydrogen or an alkyl radical having 1 to 6 carbon atoms.
A wide variety of aromatic oxides may be used to prepare the epoxide/primary amine adducts needed to produce the boron compounds in the invention. Typical aromatic oxides for use herein include styrene oxide, alpha-methylstyrene oxide, ~ara tertiary-butylstyrene oxide, cresyl glycidyl ether, ortho-methylstyrene oxide, 1,2-epoxybenzene, and para-methyl styrene oxide and mixtures thereof. It should be noted that, of all the embodiments of the invention, the most highly pre~erred are those produced by borating the intermediate reaction prod~ct of a primary amine or ammonia with styrene oxide, with the resulting boron compound havlng a ring structure wherein ethylene groups connect the nitrogen and oxygen atoms of the ring and unsuhstituted phenyl groups are attached to the carbon atom of said ethylene groups which are bonded to the oxygen atoms.
When an aromatic oxide is selected as a starting material, the primary amine may be reacted with the aromatic oxide in the presence of a solvent, for example, toluene, to produce an epoxide/amine adduct. The solvent is added in sufficient ~uantity to dissolve or disperse the reactants.
Generally, the primary amine and aromatic oxide are reacted at a pressure of from about atmospheric pressure to about 500 p.s.i.g. (35 atmospheres) at a temperature of from 176 F. (80 C.~ to 392 F.(200 C.), for 1 to 5 hours. The primary amine is preferably reacted with the aromatic oxide at a molar ratio of 1:2 to produce an epoxide/amine adduct. It may be desirable to react the primary amine with two different aromatic oxides to produce a mixed epoxide/amine adduct. In this embodiment of the invention, one mole of the primary amine is reacted with one mole each of two different aromatic oxides to produce the desired tertiary amine. Yet another method of producing the desired epoxide/amine adduct involves reacting one mole of an aromatic-substituted alkene oxide and one mole of an alkene oxide, for example ethylene oxide, with a primary amine to produce an epoxide/amine adduct having an aromatic moiety and an a]ky] moiety attached to the nitrogen atom.
Next, the epoxide/amine adduct is reacted with boric acid at a molar ratio of about 1:1, optionally in the presence of a solvent, for example, xylene, benzene, toluene, or -the ]ike, -to produce a boron~containing, heterocyclic compound of the present invention~ If a solvent is used, it will normally comprise from about 20 to about 50 weight percent, preferably from about 30 to about 40 weight percent of the reaction mixture. The reaction is conducted under reflux at a temperature of from 176 F. (80 C.) to 392 F. (200 C.), F,referably from 176 F. (80 C.) to 300 F. (148.89 C.)~ at a pressure of from atmospheric pressure to about 500 p.s.i.g.
(35 atmospheres), for about 1 to about 5 hours. The boron-containing heterocyc].ic compound thus produced will contain from about 0.5 to about 10 weight percent, pref-erably ~rom about 2 to about 5 weight percent of boron.
Typical boron-containing, heterocyclic compounds herein which contain alkyl species in the heterocyclic ring structure are selec-ted from the group consisting of methylaminod.iethylate hydrogen horate, ethylaminodiethylate hydrogen borate, propylaminodiethylate hydrogen borate, butylaminodiethylate hydrogen borate, octadecylamino~
diethylate hydrogen borate, dodecylaminodiethylate hydrogen borate, cyclohexylaminodiethylate hydrogen borate, phenyl-aminodiethylate hydrogen borate, oleylaminodiethylate hydrogen borate, cocoaminodiethylate hydrogen borate tallowaminodiethylate hydrogen borate, dodecylamino di(-2-methylethylate) hydrogen borate, and dodecylamino di(-2-phenylethylate) hydrogen borate and mixtures thereof.
Representative boron-containing, heterocyclic compounds which contain alkylaryl species on the hetero-cyclic ring structure include the following compounds:

~5'~

l-hydroxy- 3,7-diphenyl-5-dodecyl-5-aza-l-bora-2,8-dioxa-cyclooctane; l-hydroxy-4,6-diphenyl-5-dodecyl~5-aza-1-bora-2,8-dioxacyclooctane; 1-hydroxy-4,7-diphenyl-5-dodecyl-5-aza-l-bora-2,8- dioxacyclooctane; 1-hydroxy-3,7-dicresyl-5~
dodecy1-5-aza-1-bora-2,8-dioxacylooctane; 1-hydroxy-4,6-dicresyl-5-dodecyl-5-aza-1-bora-2,8-dioxacyclooctane;
l-hydroxy-~,7-dicresyl-5-dodecyl-5-aza-1-bora-2,8-dioxa-cyclooctane; l-hydroxy-3,7~dimethyl-3,7-diphenyl-5-dodecyl-5-aza-1-bora-2,8-dioxacyclooctane;l~hydroxy-~,6-dimethyl-4,6-diphenyl-5-dodecyl-5-aza-1-bora-2,8-dioxacyclooctane;
l-hydroxy-4,7-dimethyl-4,7-diphenyl-5-dodecyl-5-aza-1-bora-2,8-dioxacyclooctane; 1-hydroxy-3,7-para-tertiary-butyl-phenyl-5-dodecyl-5-aza-1-bora~2,8-dioxacyclooctane;
l-hydroxy-4,6-para-tertiary-butylphenyl~5-dodecyl-5~a~a-1-bora-2,8-dioxacyclooctane; 1 hydroxy-4,7-p--ara-tertiary-butyl-phenyl-5-dodecyl-5-aza-1-bora-2,8-dioxacyclooctane;
l-hydroxy-3,7-diphenyl-5-coco-5-aza-1-bora-2,8-dloxa-cyclooctane; and l-hydroxy-3,7-diphenyl-5-tallow-5-aza-1-bora-2,8-dioxacyclooctane and mixtures thereof. It should be noted that the methyl, ethyl, propyl, butyl, cyclohexyl, octadecyl, phenyl, steryl, oleyl, coco, tallow and the like moieties may be substituted for the dodecyl moiety in the above heterocyclic compounds.
Metal derivatives of the boron-containing, heterocyclic compounds herein are conveniently prepared by contacting the boron-containing, heterocyclic compound with a metal or metal compound, usually a metal in salt form. Thus, the metal acetates, proplonates, etc., are suitable for use. The preferred metal compound for use in incorporating the metal ion into the borate of the inven-~ 3'~

tion is the metal acetate. Generally, the heterocycliccompounds are reacted with the metal compounds in a molar ratio range of from about 1:1 to about 6:1, preferably from about 1:1 to about 4:1, at a pressure of from about atmospheric to about 500 p.s.i.g~ (35 atmospheresl and a temperature of from about 176 F. (80 C.) to about 392 F. (200 C.). Water and, in the case where metal acetates are used, acetic acid are then distilled from the reaction mixture using a water-cooled condenser. (It should be noted that not all metal salts are desirable for incorpo-rating the metal ion into the boron-containing, heterocyclic compound. The metal carbonates, nitrates, chlorides, and sulfates, to name a few, are all undesirable as vehicles for imparting metal ions into the boron-containing, heterocyclic compound. These metal salts experlence solu-bility problems and separation problems, and, in addition, undesirable ions frequently contaminate the boron-contain ing, heterocyclic compound.) Generally, the boron-contain-iny, heterocyclic compounds are reacted with the metal compounds herein in a molar ratio range of from about 1:1 to about 6:1, especially from about 1:1 to about ~:1.
Desirable metals are usually selected from transition metals having an atomic number of 21 through 30 or Group IVA metals of the Periodic Table. Transition metals which are suitable for use are selected from scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nic~el, copper and ~inc and mixtures thereof.
Suitable Group IVA metals include lead and tin and mixtures thereof. Other metals (or metalloids or semi-metals) may also be selected, such as gallium, bismuth, and antimonyO

\~
7~

Normally, the metal will comprise from about 1 to about 17 weight percent, preferably from about 5 to about 9 weight percent of the boron-containing, heterocyelic compound.
Representative metallic derivatives of the above compositions include the following compounds: copper di--(l-oxy~3-,7-diphenyl-5-dodecyl-5-aza-1-bora-2,8-dioxa-cyclooctane); copper di-(1-oxy-~,6-diphenyl-5-dodecyl-5-aza-l-hora-2,8-dioxacyclooctane); copper di-~1-oxy-4,7-diphenyl-5-dodecyl-5-aza-1-bora-2,8-dioxaeylooctane;
copper di~ oxy-3,7-dicresyl-5-dodecyl-5-aza-1-bora-2,8-dioxacyclooetane); eopper di-(1-oxy-4,6-dieresyl-5--dodeeyl-5-aza-1-bora-2,8-dioxacyclooctane); copper di-(1-oxy-4,7-dicresyl-5-dodecyl-5-aza-1-bora-2,8-dioxacyclooctane);
copper di- (l-oxy-3,7-dimethyl-3,7-diphenyl-5~dodecyl-5-aza-l-bora-2,8-dioxacyclooctane); copper di-(1-oxy-4,6-dimethyl-4,6-diphenyl-5-dodecyl-5-aza-1-bora-2,8-dioxa-cyelooctane); eopper di-(1 oxy-4,7-dimethyl-4,7-diphenyl-5-dodecyl-5-aza-1-bora-2,8-dioxacyclooetane); copper di-(1-oxy-3,7-para tertiary~butyl-phenyl-5-dodecyl-5~aza~
1-bora-2,B-dioxacyclooctane); copper di-(l-oxy-4,~ para ter-tiary-butylphenyl-5-dodecyl-5-aza-1-bora-2,8-dioxacyclo -octane); copper di-(l-oxy-4,7-para tertiary-buty]-phenyl-5-dodecyl-5-aza-1-bora-2,8-dioxacyclooctane); copper di-(l-oxy-3,7-diphenyl-5-coco 5-aza-1-bora-2,8-dioxacyclooctane);
ancl copper di-(l-oxy-3,7-dlphenyl-5-tallow-5-aza-1-bora-2,8-dioxacyclooctane). Other metals may be ineorporated into the above compounds, i.e., substituted for the copper, for example, scandium, titanium, chromium, manganese, iron, cobalt, nickel, zinc, lead and tin ancl mixtures thereof. In addition, methyl, ethyl, propyl~ butyl, cyclohexyl/ octadecyl, phenyl, steryl, oleyl r COCO~ tallow and the like moieties may be subs~ituted for the dodecyl moiety in the above-described heterocyclic compounds.
If it is desired that M in ~ormula (I) herein-before, and also for the corresponding M radical of any of the borate of the invention formulas herein, be organic, then one may employ the following procedure: the borate of the invention is reacted under conditions as set forth hereinbefore with respect to preparing metal derivatives, but instead of using a metal salt, an alcohol of choice is employed and no water is added to the reaction. For example, if a methyl radical is desired for M, then methanol is employed; if a cyclohexyl radical, then cyclohexanol; and if an unsubstituted phenyl radical, then phenol. Optionally, a solvent such as toluene or xylene is also used. After the reaction is complete, water is removed by distillation, and the desired borate oE the invention is obtained.
Another proceduxe, preferred especially for preparing borates of the invention with M as a substituted phenyl group, involves reacting the alcohol of choice, e.g., 2,6-tert-butyl phenol, optionally in the presence of a solvent such as toluene or xylene, with boric acid in the presence of an acid catalyst, e.g., para-toluenesulfonic , acid, or other organic soluble acids (e.g., acetic) or an ion exchange resin catalyst, Amberlyst 15, which is strongly acidic. The reaction may be accomplished by refluxing, which removes two moles of water for every mole of boric acid which reacts with the phenol compound. rrhe resulting product, a boric acid:phenol adduct is in turn r~7~le ~n c~

76~3~j reacted with an amine:epo~ide adduct, under conditions hereinbefore specified for reacting boric acid with an amine:epoxide adduct, and after water i~ removed by distillation, the final desired product is recovered.
Another species of the heterocyclic compounds here.in are the bisthydrocarbyloxy methylated) boron-containing, heterocycl.ic compounds. These compounds are of the following formula (IV):

l IIV) /CH2 -- CH - O \ M2+Y2 f O

_ R18 where R16 .is an inorganic radical or an organic radical having from 1 to about 50 carbon atoms , R17 and Rl~ are the same or different organic radicals having from 1 to about 50 carbon atoms, Y2 is an integer from 1 to 4, and M2 is an organic or inorganic radical but preferably is hydrogen or a metal, typically selected from a transition metal having an atomic number of 21 through 30 or a Group IVA metal as disclosed in the Periodic Table located in the Handbook of Chemistry and Physics, 46th Edition. If M2 is an organic radical, it is preferred that it be ~;~5~

chosen from the group co~sisting of substituted or unsub-stituted alkyl, alkenyl, alkynyl, aryl, arylalkyl, and alkylaryl radicals having from 1 ~o 50 carbon atoms, wlth methyl and cyclohexyl radicals being among the most preferred groups. ~lso among -the most preferred groups, if M is organic, are substituted and unsubstituted phenyl groups, with substituted phenyl yroups being particularly preferred. The phenyl group may be substituted with, for example, an acetyl group, a methyl radical, or an -O-C~13 group. One of -the most preferred substituted phenyl groups is the hindered phenyl group wherein the phenyl group is substituted at the 2 and 6 carbon a-tom of the phenyl ring with an organic group having more than 3 carbon atoms, e.g., 2,6-di-tert-butyl phenyl groups, such as 4-methyl-2,6-di-tert-butyl phenyl. ~indered phenyl groups provide the compound with hydrolytic stability. It has also been unexpectedly found that non-hindered phenyl groups, whether substituted or unsubstituted, also provide the compound with hydrolytic stability.
When Rl6, Rl7 and Rl8 are organic radicals, usually at least 65 percent, more usua]ly at least 75 percent, and most usually at least 90 percent of the atoms composing said radicals will be carbon and hydrogen atoms.
Preferably, Rl6 is hydrogen or a substituted or unsubsti-tuted alkyl, alkenyl, alkynyl, aryl, alkylaryl, or arylalkyl radical having from l to about 30 carbon atoms, and more preferably, from l to about 24 carbon atoms. On the other hand, Rl7 and Rl~ are preferably the same or different radicals selected from a substituted or unsubstituted alkyl, alkenyl, alkynyl, aryl, alkylaryl and ~ r~ t~

arylalkyl radicals having Erom 1 to about 50 carbon atoms, and more preferably from 1 to about 30 carbon atoms, more preferably still from 1 to about 20 carbon atoms, and most preferably from 1 to about 10 carbon atoms.
In preparing the bis(hydrocarbyloxy methylated) boron-containing, heterocyclic compounds, a primary amine or ammonia (but preferably a primary amine) is reacted with an alkyl, aryl, alkylaryl or arylalkyl glycidyl ether to produce a bis(hydrocarbyloxy methylated) primary amine.
Glycidyl ethers suitable for use herein preferably are of the following formula (V):

/ O\
(V) CH2 CH - CH ~- - R19 where Rlg is an organic radical ha~ing 1 to 50 carbon atoms with said organic radical in a preferred mode comprising at least 75 percent, preferably 90 percent of carbon and hydrogen atoms. Preferably, R19 is a substi-tuted or unsubstituted alkyl, aryl, alkylaryl or arylalkylradical ha~ing from 1 to about 50 carbon atoms, preferably from 1 to about 30 carbon atoms, more preferably still from 1 to about 20 carbon atoms, and most preferably from 1 to about 10 carbon atoms.
~ wide variety of glycidyl ethers may be used to prepare the oxylated primary amines needed to produce the he-terocyclic compounds hereinO Typical glycidyl ethers for use herein include methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, cresyl glycidyl ether, ~ 3 phenyl methyl glycidyl ether, ethyl phenyl glycidyl ether and phenyl ethyl glycidyl ether and mixtures thereof.
The primary amine may be reacted with the glycidyl ether in the presence of a solvent, for example, toluene to produce a dioxygenated amine. The solvent is added in sufficient quantity to dissolve or disperse the reactants.
Generally, the primary amine and glycidyl ether are reacted at a pressure of from about atmospheric pressure to about 500 p.s.i.g. (35 atmospheres) at a temperature of from 176 F. (80 C.) to 392 F. (200 C.) for 1 to 30 hours. The primary amine is preferably reacted with the ~lycidyl ether at a molar ratio of 1:2 to produce the bis(hydrocarbyloxy methylated) amine. It may be desirable to react the primary amine with two different glycidyl ethers to produce a mixed hydrocarbyloxy methylated amine. In this embodiment of the invention, one mole of the primary amine is reacted ~ith one mole each of two different glycidyl ethers to produce the desired mixed hydrocarbyloxy methylated amine. Yet another method of producing the desired amine involves reacting one mole of an aromatic glyciclyl ether and one mole of an alkyl glycidyl ether with a primaxy amine to produce an amine having an alkylaryl moiety and an alkyl moiety attached to the nitrogen atom of the amine.
Next, the bis(hydrocarbyloxy methylated) amine or mixed hydrocarbyloxy methylated amine is reacted with boric acid at a molar ratio of from about l:1, optionally in the presence of a solvent, for example, xylene, benzene, toluene, or the like, to produce a bis(hydrocarbyloxy ~5~7f~

methylated) boron-con-taining, heterocyclic compound of the present invention. Normally, the solvent, if used, will comprise from about 20 to about 50 weight percen~, pref-erably from about 30 to 40 weight percent of the reaction mixture. The reaction is conducted under reflux at a temperature of from 176 F. (80 C.) to 392 F. (200 C.), at a pressure of from atmospheric pressure to about 500 p.s.i.g. (35 atmospheres) for about 1 to about 30 hours.
The compound thus produced will contain from about 0.5 to about 10 weight percent, preferably from about 2 to about 5 weight percent of boron.
In a preferred mode the primary amine and glycidyl ether are first reacted together and the inter-mediate reaction produc-t thus produced is, next, reacted with boric acid.
An alternative method of producing the bis(hydro-carbyloxy methylated) boron-containing, heterocyclic compounds herein involves reacting the primary c~nine, glycidyl ether and boric acid in a one-step process.
Representative bis(hydrocarbyloxy methylated), boron-containing, heterocyclic compounds produced in accordance with the procedure herein include t~e following compounds: 1-hydroxy-3,7-di-(methoxymethyl)-5-dodecyl-5-aza~1-bora-2,8-dioxacyclooctane; 1-hydroxy-4,6-di-(methoxy methyl)-5-dodecyl-5-aza-1-bora-2~8-dioxacyclooctane;
1-hydroxy-3,7-di-lethoxymethyl)--5-dodecyl-5-aza-1 bora-2,8-di~xacyclooctane; 1-hydroxy-3,7-di-(propoxymethyl)-5-dodecyl 5-a~a-1-bora-2,8-dioxacyclooctane;l-hydroxy-4,6-di-(butoxymethyl~-5-clodecyl-5-aza-1-bora-2,8~dioxacyclo-octane; 1-hydroxy-3,7 di-(methylphenoxymethyl)-5-dodecyl--i(3~;

5-aza-l-bora-2,8-dioxacyclooctane; 1-hydroxy-4,6-di-(methyl-phenoxymethyl)-5-dodecyl-5-aza-1-bora-2,8~dioxacyclooctane;
1-hydroxy-3,7-di-(ethylphenoxymethyl)-5-dodecyl-5-aza-1-bora-2,8-dioxacyclooctane; l-hydroxy-4,6-di-(phenylmethoxy-methyl)-5-dodecyl-5-aza-1-bora-2,8- dioxacyclooctane; and 1-hydroxy-3,7-di (phenylethoxymethyl)-5-dodecyl-5-aza-l-bora-2,8-dioxacylooctane and mixtures thereof. It should be noted that the methyl, ethyl, propyl, butyl, cyclohexyl, octadecyl, phenyl, steryl, oleyl, coco and tallow moieties may be substituted for the dodecyl moiety in the above heterocyclic compounds. This embodiment o~ -the i~vention has the added advantage o~ enhanced extreme pressure properties and a more pleasant odor.
Metal derivatives of the bis(hydrocarbyloxy methylated), boron-containing, heterocyclic compounds, herein are conveniently prepared by contacting -the compound with a metal, usually in salt form. Thus, the metal acetates, proprionates, etc., are suitable for use. The preferred metal compound for use in incorporating the metal ion into the bis(hydrocarbyloxy methylated) boron-containing, heterocyclic compound is the metal acetate~
Generally, these compounds are reacted with the metal compounds in a molar ratio range of from about 1:1 to about 6:1, preferably from about 1:1 to about ~:1, at a pressure of from about atmospheric to about 500 p.s.i.y.
(35 atmospheres) and a temperature of from about 176 F.
(80 C.) to about 392 F. (200 C.). Water ancl, in the case where metal acetates are used, acetic acid are distilled from the reaction mixture using a water-cooled condenser.

Representative of the metal compounds are: copper cli[-l-oxy-2,7~di-(me-thoxymethyl~-5-dodecyl-5-aza-1-bora-2,8-dioxacyclooctane]; copper di-[l~oxy-4,6-di~methoxy-methyl)-5-dodecyl 5-aza-1-bora-2,8-dioxacyclooctane];
copper di-[l-oxy-3,7-di-(ethoxymethyl)-5-dodecyl~5-aza-1-bora-2,8-dioxacyclo-octane]; copper di-[1-oxy-3,7-di-(pro~
poxymethyl)-5-dodecyl~5 aza l~bora~2,8~dioxacyclooctane];
copper di~[l~oxy~4,6-di~(butoxymethyl)~5~dodecyl~5-aza~l~
bora~2,8-dioxacyclooctane]; copper di--[]-oxy~3,7 di~(methyl-phenoxymethyl)-5~dodecyl~5-aza-l~bora-2,~dioxacyclooctane];
copper di~[l-oxy-4,6 di-(methylphenoxymethyl~-5-dodecyl~5-aza-l-bora-2,8~dioxacyclooctane]; copper di-[1-oxy-3,7-di(ethylphenoxymethyl)-5-dodecyl-5~aza-1-bora 2,8-dioxa-cyclooctane]; copper di-[l-oxy-4,6-di(phenylmethoxymethyl)-5-dodecyl-5-aza-l~bora-2,8~dioxacyclooctane]; and copper di [l-oxy~317-di-(phenyl-ethoxymethyl)~5~dodecyl-5-aza-l-bora~2,a-dioxacyclooctane] and mixtures thereof. Other metals may be incorporated into the above compounds, i.e., substituted for the copper, for e~ample, scandium, titanium, vanadium, chromium, man~anese, iron, cobalt, nickel, zinc, lead and tin and mixtures thereof. Semi-metals and metalloids may also be incorporated into such compounds.
In addition, methyl, ethyl, propyl, butyl, cyclohexyl, octadecyl, phenyl, steryl, oleyl, coco and tallow moieties may be substituted for the dodecyl moiety in the above-described compounds.
It should be noted that the foregoing bis(hydro-carbyl methylated) boron-containing compounds of formula lIV) have been found to be soluble in 450 neutral oil, at least when prepared with tallowamine ox cocoamine. However, the higher cost of preparing such compounds, particularly in comparison to compounds of formula (II) structure prepared with styrene oxide, makes the latter, i.e., the formula (II) compounds prepared from styrene oxide, a more preferred additive for automotive lubricating engines.
Also suitable herein are sulfohalogenated, boron-containing, heterocyclic compounds of the following formula (VI):

X
r I /R38 \

L f \ R39 - O ~ y7 (VI) (S)n2 . ~ /R40 \ .
R36 f~ R37 N \ / B O M8+Y8 Xl Y~3 wherein R3~ and R36 may be the same or different organic or inorganic radicals but more typically R34 and R36 as well as R35 and R37 are the same or different organic radicals having from about 1 to about 30 carbon atoms, R38~ R39, R40 and R41 are the same or different organic radicals having from about 1 to about 50 carbon atoms, n2 is an integer from 1 to 4, preferably 1 or 2, X and X1 are halogens independently selected from the group consisting of chlorine, fluorine, bromine and iodine and mixtures thereof, with chlorine being especially preferred. The 34, R35, ~36 and R37 are typically s~lected from the same or different, substituted or unsubstituted hydrocarbyl groups, such as, substituted or unsubstituted aliphatic and aromatic groups, particularly the alkyl, alkenyl, alkynyl, aryl, alkylaryl or arylalkyl radicals having from about 1 to about 30 carbon atoms, preferably from about 1 to about 20 carbon atoms. The organic als P~3g, R39, R40 and R41 are typically selected from the same or different, substituted or unsubstituted hydrocarbyl groups, such as, substituted or unsubstituted aliphatic and aromatic groups, particularly the alkyl, alkenyl, alkynyl, aryl, alkylaryl, or arylalkyl radicals having from about l to about 50 carbon atoms, p.referably from about 1 to about 30 carbon atoms. Preferably R38, R39, R40 and R41 are alkylaryl or arylalkyl having from about 8 to about 30 carbon atoms. More preferably, R3~, R39, ~40, and R41 are alkylaryl groups and, most preferably, are alkylaryl groups wherein ethylene radicals connect the nitrogen and oxygen atoms and unsubstituted phenyl radicals are bonded to the carbon atoms of the ethylene radicals bonded to the oxygen atoms. y7 and Y8 are the same or different integers from 1 to 4, and M7 and M8 may be an organic or inorganic group, but preferably are either hydrogen or a metal with the metal typically a transition metal having an atom.ic number from 21 to 30 or a Group IVA
metal of the Periodic Table or mixtures thereof. If M7 or M8 is an organic radical, it is preferred that it be chosen from the group consisting of substituted and unsubstituted alkyl, alkenyl, alkynyl, aryl, arylal.kyl, a.nd alkylaryl radicals of between 1 and 50 carbon atoms, ~ ra~

with methyl and cyclohexyl radicals beiny among the most preferred groups. Also among the mos-t preferred groups, if M is organic, are substi~uted and unsubstituted phenyl groups, with substituted phenyl groups being particularly preferred. The phenyl group may be substituted with, ~or example, an acetyl group, a methyl radical, or an -O-CH3 group. One of the most preferred substituted ph~nyl groups is the hindered phenyl group wherein the phenyl group is substituted at the 2 and 6 carbon atom of the phenyl riny with an organic group having more than 3 carbon atoms, e.g., 2,6-di-tert-butyl phenyl groups, such as 4-methyl-2,6-di-tert-butyl phenyl. ~lindered phenyl groups provide the compound with hydrolytic stability. It has also been une~pectedly found that non-hindered phenyl groups, whether substituted or unsubstituted, also provide the compound with hydrolytic stability. M7 and ~8 may be the same physical atom or species, e.g., the two borated radicals may be attached to the same metal atom or to-gether may be one organic radical~
~lalogenated, boron-containiny, heterocyclic compounds useful in the present invention are of the following formula (VII):
~ 2 X3 /

(VII) ~2 IH C~l - R43 - N \ \ B - O Mg Y9 Yg wherein R~2 may be an inorganic radical bu-t more typically R~2 and R~3 are the same or different organic radicals -32~

having from about 1 to about 30 carbon atoms, R44 and R45 are the same or different organic radicals having from about 1 to about 50 carbon atoms, X2 and X3 are halogens selected from the group consisting of chlorine, fluorine, bromine and iodine and mixtures thereof, with chlorine and bromine being especially preferred. The radicals R42 and R43 are typically selected from the same or different/
substituted or unsubstituted hydrocarbyl groups, such as substituted or unsubstituted aliphatic and aromatic groups, particularly the alkyl, alkenyl, alkynyl, aryl, alkylaryl or arylalkyl radicals having from about 1 to about 30 carbon atoms, preferably from about 1 to about 20 carbon atomsO The organic radicals R44 and R45 are typically selected from the same or different, substituted or unsubstituted hydrocarbyl groups, such as, substituted or unsubstituted aliphatic and aromatic groups, particularly the alkyl, aryl, alkylaryl or arylalkyl radicals having from about 1 to about 50 carbon atoms, preferably from about 1 to about 30 carbon atoms. Preferably, R4~ and R45 are alkylaryl or arylalkyl having from about 8 to about 30 carbon atoms. More preferably, R44 and R45 are alkylaryl groups and, most preferably, are alkylaryl groups wherein ethylene radicals connect the nitrogen and oxygen atoms and unsubstituted phenyl radicals are bonded to the carbon atorns of the ethylene radica1s bonded to the oxygen atoms.
yg is an integer from 1 to 4, and Mg may be an organic or inorganic group, but preferably i5 either hydrogen or a transition metal having an atomic number between 21 and 30 or a Group IVA metal of the Periodic Table and mixtures thereof. If Mg is an organic radical, it i~ preferred .;t)~

that it be chosen from the group consisting of substituted and unsubstituted a]kyl, alkenyl, alkynyl, aryl, arylalkyl, and alkylaryl radicals of between 1 and 50 carbon atoms, with methyl and cyclohexyl radical being among the most preferred groups. A]so amon~ the most preferred groups, if M is organic, are substituted and unsubstituted phenyl groups, with substituted phenyl groups being particularly preferred. The phenyl group may be substituted with, for example, an acetyl group, a methyl radical, or an -O-CH3 group. One oE the most preferred substituted phenyl groups is the hindered phenyl group wherein the phenyl group is substituted at the 2 and 6 carbon atom of the phenyl ring with an organic group having more than 3 carbon atoms, e.g., 2,6~di-tert-butyl phenyl groups, such as 4-methyl-2,6-di-tert-butyl phenyl. Hindered phenyl groups provide the compound with hydrolytic ~tability. It has also been unexpectedly found that non-hindered phenyl groups, whether substituted or unsubstituted, also provide the compound with hydrolytic stability.
~alogenated boron-containing, heterocyclic com-pounds typically include 1-hydroxy-3,7-diphenyl--5-(9-10-dichlorooctadecyl)-l-bora--2,8-dioxa 5-aza-cyclooctane;
1-hydroxy-3,7-diphenyl-5-(9-10-dichlorostearyl)-1-bora-2,8-dioxa-5-aza-cyclooctane; and 1-hydroxy-3,7-diphenyl-5 (dichlorotallow)-1-bora-2,8-dioxa-5-aza-cyclooctane ancl mixtures thereof. Other halogens which may be substituted for the chlorine above include fluorine, bromine and iodine and mixtures thereof.
Sulfurized forms of the borate of the invention are of the following formula (VIII):

- -R55 0\ Y1o ~VIII) ~54 N\ B O Mlo R56 - O ylO

wherein R5~ is an inorganic or organic radical, R55 and R56 are the same or different organic radicals, and M1o is an organic or inorganic radical, with Y1o being the valence of M1o, and preferably an integer from 1 to 4, further provided that at least one of R54, R55, R56, and M1o contains sulfur. Thus, for example, one or more of R54, R55, R56, and M1o may contain a "sulfide group,"
which is herein defined as sulfur bonded (1) as an end group as represented by a thio-group (-SH), ~2) as part of the compound backbone (-CHX-S-CHx-), (3) as a pendant from the compound as represented by an episulfide group /s~
(-CHX CHX ) or (4) one or more sulfide or polysulfide bridges ( - S
or ~S(n~~, wherein ~S(n)~ represents two or more sulfur atoms bonded in series) connected to an organic radical, including another organic radical in formula (VIII) and an organic radical in a second borate of the invention of formula (VIII) structure or any of the borates of the invention previously illustrated by formula.
The preferred sulfurized borate of the invention contains a sulfide or polysulfide bridge connecting two borates of the invention, with the most preferred location of the bridge being between the two side R groups, i.e., as shown in -the following formula (IX):

,t~i / 58 \ Y
l R59 O , Mll (IX) (S)nl Yll ¦ / 61 \ l Y12 \ R 6 2 /

wherein all of the R groups are the same or different organic radicals and Mll and M12 are the same or different organic or inorganic radicals and (S)nl represents one or more sulfide or polysulfide bridges connecting R57 and R60 .
As shown in formula (IX), one or more sulfur bridges exist between two borates of the invention.
~Iowever, it is further contemplated in the invention that the sulfurized borate of the invention may have three or more borates of the invention, each of formula (VIII) structure wherein the R side groups (shown in formula (VIII) as R54) and the M radicals of the borates of the invention may be the same or different inorganic or organic radicals and the R groups bridging the oxygen and nitrogen atoms (shown in formula (VIII) as R55 and R56) are the same or different organic radicals. It is most highly preferred that all sulfur bridges in the borate of the invention connec-t the R group side chains ~R54 in formula (VIII) and R57 and R60 in formula (IX)) emanating from the nitrogen atom of each borate of the invention, in which case the R group side chains would all be organic ~l~5~

radicals. Ilowever, it is also contemplated in alternative embodiments that the sulfur bridge could connect elsewhere, e.g., from the R group side chain to M, from one R group connecting an oxygen and nitrogen atom to another, etc.
In formulas (VIII3 and (IX), R54, R57, and R60 are preferably organic radicals, usually having from 1 to 50 carbon atoms, and may, for example, be a substituted or unsubstituted hydrocarbyl group~ particularly an alkyl, alkenyl, alkynyl, aryl, alkylaryl, or arylalkyl radical having from 1 to 30 carbon atoms, often from about 9 to 20 carbon atoms- R5s~ R56~ R58~ R59~ R61' 62 generally organic radicals of 1 to 50 carbon atoms, and may, for example, be a substituted or unsubstituted hydrocarbyloxy group, e.g., the structure bridging the nitrogen and oxygen atom in formula (IV), or a hydrocarbyl group such as an alkyl, alkenyl, alkynyl, aryl, alkylaryl, or arylalkyl radical. Preferably, R55, R56, R58, R
R61, and R62 are alkylaryl groups wherein ethylene radicals connect the nitrogen and oxygen atoms and unsubstituted phenyl radicals are bonded to the carbon atoms of the ethylene radlcals bonded to the oxygen atom.
Mlor Mll, and M12 are typically inorganic radicals such as hydrogen or a metal having an atomic number from 21 to 30, or a Group IVA metal. Other metals (or metalloids or semi-metals~ may also be selected, such as gallium, bismuth, and antimony. Mlo, Mll, and M12 may also be organic radicals, preferably chosen from substi-tuted or unsubstituted alkyl, alkenyl, alk.ynyl~ aryl, arylalkyl, and alkylaryl radicals with methyl and cyclo-hexyl radicals being among the mos-t preferred. Also among ~ ~r t~J~

the most preferred groups, if M is organic, are substituted and unsubstituted phenyl groups, with substituted phenyl groups being particularly preferred. The phenyl group may be substituted with, for example, an acetyl group, a methyl radical, or an -O-CH3 group. One of the most preferred substituted phenyl groups is the hindered phenyl group wherein the phenyl group is substituted at the 2 and 6 carbon atorn of the phenyl ring with an organic group having more than 3 carbon atoms, e.g., 2,6 di-tert-butyl phenyl groups, such as 4-methyl-2,6-di-tert-butyl phenyl.
Hindered phenyl groups provide the compound wlth hydrolytic stability. It has also been unexpectedly found that non-hindered phenyl groups, whether substituted or unsubstituted, also provide the compound with hydrolytic stability. Also, Mll and M12 may be the same physical atom or species, e.g., the two borate radicals may be attached or bonded to the same metal atom or together may be one organic radical.
One of the advantages of the sulfurized form of the borates of the invention is that of increased oxidation stability, as well as substantially enhanced extreme pressure properties. Generally, the sulfurized compounds exhibit the same or superior extreme pressure properties when used at weight percen-t concentrations substantially less than other heterocyclic, boron-containing compounds disclosed herein.
The sulfurized, halogenated or sulfohalogenated compounds herein are produced in accordance with the procedure described before for producing -the boron-contain-ing, heterocyclic compounds with the added stipulation

3 d that the primary amine used to form the heterocyclic compound is unsaturated. Elemental sulfur is reacted with the heterocyclic compound in toluene, xylene, or the like to produce a sulfurized compound. The sulfohalogenated form of the compound may be produced by substituting a sulfur halicle for the elemental sulfur above, for example, a sulfur chloride such as sulfur monochloride, sulfur dichloride, etc. The halogenated form of the heterocyclic compound is produced by substituting a halogen for the sulfur above.
The sulfurized compounds of the invention are preferably prepared by reacting one mole of sulfur with one equivalent of unsaturateds in the R side group of the boron heterocyclic compound or its metal derivative. For example, if l-hydroxy-3,7-diphenyl-5-tallow-5-aza-l~bora-2,8-dioxacyclooctane is the chosen boron compound to be sulfurized, then 1 mole of sulfur is reacted with about 2.5 moles of the boron compound (because the boron compound contains about 0.40 equivalents of unsaturateds in the ~ group side chain). The reaction is conducted in the presence of a solvent such as toluene or xylene, usiny at least 3 moles of solvent for every mole of boron compound reacted. The reaction is conduc-ted at elevated temperature with refluxing, with the time and temperature of reaction being dependent to a great extent upon the solvent chosen. If toluene, sulfurization is usually achieved in four hours at 110 C. under atmospheric pressure conditions; if xylene, then sulfurization is more rapid, occurring in 1 hour of refluxing at 137 to 140 C.
under atmospheric pressure conditions. To prevent ~ ~rjDJ~

oxidation of the sulfur during said reactions, an inert gas blanket, such as nitrogen or argon, may be employed.
In an alternative embodiment of the invention, the elemental sulfur is first reacted with the unsaturated primary amine followed by subse~uent reaction with the desired epoxide, which is in tuxn followed by reaction with boric acid. Alternative].y still, an unsaturated amlne:epoxide adduct may be produced first, followed by reaction with the elemental sulfur, which is in turn followed by reaction with boric acid. Reaction conditions for these embodiments typically are commensurate with those specified above for sulfurization reactions, reac-tions with boric acid, and reactions between amines andepoxides.
As stated above, the sulfurized versions of the borates of the invention typically form one or more sulfur bridges between R side groups emanating from the nitrogen atom. Such sulfur bridges, which may contain one sulfur atom or several in series, typically bond to carbon atoms immediately adjacent to a phenyl ring or alkenyl or alkynyl unsaturation. In other words, the sulfur bridge connects one R side group of a first borate of the invention with that of a second at locations formerly occupied by benzylic hydrogen (in the case of phenyl unsaturation) or an allylic hydrogen (in the case of alkenyl or alkynyl unsaturation). Thus, it will be understood that, by "unsaturateds" in the R side group, it is meant in the present specification and claims the number of allylic and benzylic hydrogens available in said R side group for substitution by a sulfur atom. And since the R side group originates in the primary amine, it will be understood that "unsaturated" in the term "unsaturated primary amine"
refers to the number of allylic and benzylic hydrogens available in the R group of the amine (of formula RNH2) for substitutlon by a sulfur a-tom.
(~f course, it will also be understood that, if the R groups connecting the nitrogen and oxygen atoms contain significant allylic and benzylic hydrogens, some bonding of sulfur a-toms at such locations may also occur.
But in the preferred embodiment, wherein styrene oxide is the epoxide chosen for reaction with the amine, and particularly when the phenyl ~roups of said styrene oxide ultimately are attached to the carbon atoms of the hetero-cyclic ring nearest the oxygen atoms, sulfur substitution is minimal, being impeded structurally by the ring itself and the influence of the oxygen atom.~
If desired, the sulfurization of the boron compound may be hastened by use of a vulcanization catalyst.
The presently preferred catalyst is zinc bis(clibutylthio-carbamate), which is employed in the reaction mixture in aratio to the boron compound of 0.01 to 0.50 moles for each mole of the boron compound.
The sulfohalogen compounds of the invention are prepared in a similar manner to the sulfurized versions, with the exception that no solvent is employed and, instead of sulfur as a reactant, a compound such as a sulfur monochloride (S2Cl2) is employed. The molar ratio of sulfur monochloride to boron compound is preferably the same as that for the sulfur to boron compound ratio employed in preparing the sulfurized species.

~41-The halogenated species of the invention is typically prepared by introducing the boron compound to be halogenated, said boron compound containing an unsaturated R side group emanating from the nitrogen atom, in-to a 450 neutral oil or into a chlorinated hydrocarbon, e.g., carbon tetrachloride, followed by bubbling of ch]orine or ~luorine into the mixture at room temperature (25 C.). Generally, the bubbling takes place for about 15 minutes, but longer times are also suitable. If bromine is the desired halogen, it is added to the mixture in liquid form, in sufficient amoun-t to saturate a portion of or all the unsaturated sites of the R side group. Bromination of the boron compound can take place in as little as lO minutes at 120 C. at atmospheric pressure. If iodine is the desired halogen, the procedure is modi~ied by adding the iodine in sufficient quantity to saturate the unsaturated sites.
Sulfohalogenated, boron-containing, heterocyclic compounds include 10,10'-dithiodi[9 chloro-1-(5-hydroxy-3,7-diphenyl-1-aza 4,6-diocta~5-bora-cyclooctyl)-octadecane];
20 dithiodi[l-(5-hydroxy-3,7-diphenyl-1-aza-4,6-diocta-5-bora-cyclooctyl) chlorotallow]; and dithiodi[l-(5-hydroxy-3,7-diphenyl-l-aza-~,6-diocta-5--bora-cyclooctyl)chlorosoya]
and mixtures thereof. It should be noted that fluorine, bromine and iodine may be substituted for the chlorine above.
It will be noted in the foregoing descriptions related to the preparation of boron heterocyclic compounds of the invention that such descriptions relate to preparing the compounds with solvents present during both reactions, i.e., the reaction of a primary amine with an oxygen-containing organic compound followed by the reaction of the resulting in-termediate product with boric acid, which yields the borated compound of the invention However, the preferred embodiment of the invention as presently contemplated is that the borated compound o~ the lnvention be produced without any solvent being employed during these two reactions. (It is, however, preferred that, when preparing the sulfurized borated compounds previously described, the sulfurizing step using elemental sulfur be carried out in the presence of a solvent, e.g., toluene.) The reason that the absence of solvent is preferred is -that it has been discovered that a more complete reaction to the desired borated product is accomplished when no solvent is emplo~ed. The presence of solvent tends to yield a mix of undesired and desired borates of the invention whereas the absence of solvent tends to selec-tively yield the desired borate of the invention.
The borates of the invention have, as stated previously, excellent extreme pressure, anti-wear, and friction-reducing properties. However, they have also been found to increase the corrosiveness of automotive lubricating engine oils, with the degree of corrosiveness depen~ing on the purity of the borate of the invention employed, the amount employed, and the particular borate of the invention chosen. Some borates of the invention herein are less corrosive than others; for example, a borate of the invention of formula (I) structure herein-before, wherein Rl and R2 are ethylene groups, is more corrosive than the borate of the invention of formula (II) 30 structure wherein P~4, R7, R~, Rg, R1o, and R11 are -~3 ~5~6~)~

hydrogen ancl R5 and R6 are both unsubstituted phenyl radicals. On the other hand, some of the sulfurized borate of the invention compounds described hereinbefore are significantly more corrosive than either of the aforementioned formulae (I) and (II) compounds, but this disadvantage is compensated for by the fact that only about one-half as much of the sulfurized compounds is needed to provide similar anti-wear, friction-reducing, and extreme pressure properties as said formulae (I) and (II) compounds.
In any event, if it is desired to lessen the corrosiveness of the borates of the invention, the lubri-cating oils into which they are added may be further provided with one or more corrosion inhibitors. Such corrosion inhibitors should impart lead and/or copper corrosion-inhibiting properties, and this because the bearings in automotive engines typically contain lead and/or copper.
In one embodiment of the present invention, copper corrosion in engine bearings is inhibited by adding to the lubrication composition a corrosion inhibiting amount, normally from 0.001 to about 5 weight percent, preferably from 0.005 to about 2.5 weight percent of a hydrocarbon polysulfide derivative of 2,5-dimercapto-1,3,4-thiadiazole having the formula (X):
N N
Il 11 (X) ~6 (S)w - C f _ (S) - P~

S

_4a~_ ~ 3~i wherein R~6 and ~7 are the same or different moieties selected from hydrogen or straight or branched chain alkyl, cyclic or alicyclic alkyl, aryl, alkylaryl or arylalkyl radicals having from 2 to about 30 carbon atoms, and w and z are integers from 1 to 8. It should be noted that R~6 ancl R47 cannot both be hydrogen because the compound would be rendered insoluble in lubricating oils.
Thus, when R46 is hydroyen, R47 must be selected from one oE the other moieties described above, and vice versa.
Suitable among such compounds are polysulfides of 1,3,4-thiadiazole-2,5-bis(alkyl, di, tri or te-tra sulfide) containing from 2 to about 30 carbon atoms.
Desirable polysulfides include 1,3,4-thiadiazole-2,5-bis(octyldisulfide); 1,3,4-thiadiazole-2.,5-bis(octyltri~
sulfide); 1,3,4-thiadiazole- 2,5-bis(octyltetrasulfide);
1,3,4-thiadiazole-2,5-bis(dodecyldisulfide~; 1,3,4-thia-diazole-2,5-bis(dodecyltrisulfide); 1,3,4~thiadiazole-2,5-bistdodecyltetrasulfide); 2-lauryldithio 5-thio~
methyl-styryl-1,3,4-thiadiazole; 2~1auryltrithio~5~thio~
alpha~methyl~styryl~1,3,4-thiadiazole; 2~mercapto-5~octyl~
dithio-1,3,4~thiadiazole and 2-mercapto-5 dodecyldithio-1,3,4-thiadiazole and mixtures thereof.
~ small amount of terephthalic acid is effective as a lead corrosion inhibitor herein. The terephthalic acid may be prepared in accordance with conventional techniques and apparatus. Generally, the terephthalic acid is incorporated into lubricating oils at a concentra-tion of from about 0.001 to about 1 weight percent, especially from about 0.005 to about 0.05 weight percent.

~45 An oxidation inhlbitor may also be employed in conjunction wi-th the desired boron heterocyclic compound or in conjunction with the boron heterocyclic compound and corrosion inhibitors. Oxidation inhibitors are typically added to lubricating oils to prevent oxidative deterlora-tion of organic materials. Any oxidation inhibitor known in the art may be employed, with suitable oxidation inhibitors being selected ~rom the group consisting of bis(dithiobenzil) metal derivatives; sulfur bridged, bis(hindered phenols); and alkyl or diakyl, diphenyl-amines, dithiocarbamates and mixtures thereof. These compounds effectively limit or prevent the attack of oxidants on copper/lead metal. In addition, these com-pounds also help to control oil oxidation as manifested by reduced sludge and varnish formation, and by reduced oil thickening.
The bis~dithiobenzil) metal derivatives herein preferably ha~e the formula (XI):

, _ S S
(XI) L~ I - c~ Mlo+t H t wherein Mlo is a first row transition metal and t is an integer from 1 to 4. Suitable transition metals include vanadium, chromium, manganese, iron, cobalt, nickel, copper, zincr preferably iron, cobalt and nickel.
The bis(dithiobenzil) metal derivatives may be prepared, for example, by reacting benzoin with a phos-phorus sulfide in the presence of dioxane at elevated temperature to produce the thiophosphoric ester of dithio-benzoin. The desired divalent metal, for example, ~46-metallic halide, is reacted with the above-described thiophosphoric ester oE dithiobenzoin to produce the bis(dithiobenzil) metal derivative.
It should be noted that the bis(dithiobenzil) metal derivatives herein do not readily dissolve in lubricant compositions. However, when the bis(dithiobenzil) metal derivatives are mixed with the boron-containing, heterocyclic compounds herein, especially dodecylaminodi-(phenylethylate) hydrogen borate, the mixture goes into solution in lubricant compositions such as motor oils.
The sulfur bridged, bis hindered phenols herein preferably have the formula (XII):

(XII) [~O ~ (CH2)2 C-- O - (CH2)2 ~ S

wherein R48 and R49 are selected from the same or different alkyl groups having from 1 to 6 carbon atoms.
Sulfur bridged, bis(hindered phenols) which are suitable for use as anti-oxidants include thiodiethyl bis(3,5-dimethyl~4-hydroxy) hydrocinnamate; thiodiethyl-bis(3,5-diethyl-4-hydroxy) hydrocinnamate; thiodiethyl bis(3,5-dipropyl-4-hydroxy) hydrocinnamate; thiodiethyl bis(3,5-dibutyl 4-hydroxy) hydrocinnama-te; thiodiethyl bis(3,5-dipentyl-4-hydroxy) hydrocinnamate and thiodiethyl bis(3,5-dihexyl-4-hydroxy~ hydrocinnamate and mixtures thereof.

1~5~6~

One unexpected result in the present invention is that, when a sulfur-bridged, bis hindered phenol is employed as an oxidation inhibitor in the present invention, lt further functions to reduce the corrosiveness of the boron compounds of the invention towards lead and copper automotive bearings. This discovery, which is illustrated hereinafter in Examples 54 to 60, permits one, through the introduction of a single additive, to take simultaneous advantage of two desirable properties -- corrosion inhibi-tion and oxidation inhibition.
Amines which are suitable for use asanti~oxidants or oxidation inhibitors herein have the formula IXIII):

(XIII) R El R53 wherein R52 and R53 are hydrogen or the same or different alkyl radicals having from about 1 to about 30 carbon atoms, preferably from about 1 to about 20 carbon atoms, with at least one of R52 and R53 being an alkyl group (most preferably unsubstituted) having from about 1 to about 30 carbon atoms, e.g., 8 carbon atoms.
Generally, the anti-o~idants herein are incorpo-rated into lubricant compositions at concentrations of from 0.01 to about 2 weight percent, preferably from 0.025 to about 0.10 weight percent, sometimes up to 1.0 weight percent.
It has also been found that the presence of copper compounds, dissolved in an automotive engine oil ~L~5~

with borates of the invention, provides for enhanced anti-wear properties. This embodiment of the invention allows for the use of less of the borate of the invention for the same level of desired anti-wear protection. The preferred compounds for this use are copper carboxylates, such as copper naphthenate, in concentrations of about lO0 to 125 wppm as Cu. However, even higher concentrations may be used, for example, up to about 3 percent by weight if desired.
This embodiment of the invention has an additional advantage in that copper carboxylates, such as copper naphthenate, has anti-oxidant properties. Other copper compounds also ~unction in this manner, e.g., copper oleate.
And in U.S. Patent 4,122,033, teachings are presented for employing copper compounds as anti-oxidants. Thus, the use of copper compounds having anti-oxidant properties functions in two ways in lubricating oils, first, as an anti-oxidant and, second, for enhancement of the anti-wear properties of the borate of the invention.
In addition to providing enhanced anti-wear properties, it has also been found tha-t a lubrication oil comprising a borate of the invention, and particularly a sulfurized borate of the invention, with an oil-soluble copper compound exhibits anti-oxidant properties better than expected in comparison to the anti-oxidant properties of a lubrication oil comprising either the borate or copper compound alone.

.~S _ a~ g ~L~57~

The invention wi]l be further described with reference to the following examples, which are intended to illustrate -the invention, not to limit the claims.

Example 1 A boron-con-taining, heterocyclic compound is prepared by adding 20 grams of boric acid, 95 grams of Armak Ethomeen C/12 [bis(2-hydroxyethyl) cocoamine] and 250 ml of toluene to a single-necked one liter round-bottomed flask. The toluene acts as a solvent and as anazeotrope for water produced during the reaction. It should be noted that boric acid is not soluble in toluene ~D"~ or Ethomeen C/12. The flask is placed in a heating mantle and fitted with a Dean-Stark trap that is topped with a condenser. The mixture thus formed is then heated until it begins to reflux. Next~ the mantle is adjusted to give a moderate reflux rate. The reaction mixture is refluxed for one hour, or until the stoichiometric amount of water (12 ml.) collects in the Dean-Stark trap and all of the boric acid has dissolved, after which the toluene is distilled from the reaction product. The reaction product (103 grams) has a clear golden color and is a fluid liquid while hot but sets into a soft viscous material when cooled to room temperature. The compound is readily soluble in hydrocarbon solvents.

Example 2 A boron-containing, heterocyclic compound is prepared by the following the procedure of Example 1 with the following substitution:

e ~ r~

1~76~i Armak Ethomeen T/12 [bis~2-hydroxyethyl) tallow-amine] is substituted for the Armak Ethomeen C/12.
Substantially the same resu~ts are ob-tained.

Example 3 A boron-containing, heterocyclic compound is prepared by mixing 20 grams of boric acid, 115 grams of Armak Ethomeen 18/12 [bis~2-hydroxyethyl) octadecylamine]
ancl, as a solvent, 250 ml of toluene in a single-necked one liter round-bottomed flask. The flask is placed in a heating mantle and fitted with a Dean-Stark trap and water-cooled condenser. The mixture is heated under reflux for one hour, during which 12 ml of water collects in the Dean-Stark trap. The toluene is then distilled from the reaction product. The resulting compound is readily soluble in hydrocarbon solvents.

Example 4 The procedure of Example 3 is followed to prepare a boron compound of the invention with the follow-ing exception: N,N-diethanol-n-methylamine (~6.3 grams) is substituted for the Armak Ethomeen 18/12. The reaction product thus produced is a liquid product with the consis-tency of honey when hot and becomes a waxy semi~solid when cooled to room temperature.

Example 5 Boric acid (20 grams), M,N-diethanol-N-phenylamine (~6.3 grams) and 250 mls of toluene are mixed in a one liter single-necked flask to prepare a boron--containing, hetero-cyclic compound. The flask is equipped with a heatincJ
mantle, ~ean-Stark trap and water-cooled condenser. The mixture is heated under reflux until the reaction is completed (12 ml of water collects), approximately one hour, and the toluene is distilled from the reaction mixture. The product thus prepared is suitable for use an extreme pressure, antiwear and friction-reducing additive for lubrication compositions.

Example 6 A metal derivative of the reaction product yielded in Example 1 is prepared by mixing 54 grams of the product of Example 1, 400 ml of toluene, 24.6 grams of nickel acetate and 150 ml of methanol in a single-necked, one liter round-bottomed flask which is equipped with a hea-ting mantle and water-cooled condenser. The mixture is refluxed for four hours. Next, water, toluene, methanol and acetic acid are distilled from the reaction product.
The product (59 grams) contained 7.8 weight percent nickel as determinecl by emission spectroscopy and the resulting product is a fluid green liquid when hot, which turns into a solld upon cooling to room temperature. The product is readily soluble in hydrocarbon solvents.

Example 7 A metal derivative of the compound of E~ample 2 is prepared by mixing the reaction product of Example 2 (54 grams), 400 ml of toluene~ 24 grams of nickel acetate and 150 mls of methanol in a single-necked, one-liter round-bottom flask, equipped with a heaking mantle, Dean-~ ~3-J~

Stark trap and water-cooled condenser. The mixture is refluxed for four hours and the toluene, water and acetic acid are distilled from the reaction product.

Example 8 A zinc derivative of the reaction product of Example 1 is prepared by mixing 5~ grams of said reaction product with ~00 ml of toluene, 19.1 grams of zinc acetate and 50 ml of methanol in a single-necked, one-liter round-bottom flask, equipped with a heating mantle and water-cooled condenser. The mixture is refluxed for four hours and the toluene, methanol, water and acetic acid are distilled. The resulting product is suitable for use as an extreme pressure, anti-wear, friction-reducing additive for lubrica-ting compositions.

Example 9 Another metal derivative is prepared by following the procedure of Example 7 with the following exception:
zinc acetate is substituted for the nickel acetate.

Example 1 0 The extreme pressure, anti-wear and friction-reducing additives produced in Examples 1 and 6 in a 1:1 ratio mixture are mixed with ~50 neutral oil and evaluated for performance~ The additive mixture is mixed with the ~50 neutral oil at 5 weight percent based on the total weight of the lubricant composition. This oil mixture is compared to Arco graphite lubricant and ASTM high reference ~s~o~
oil, SAE 20W/30 for friction xeduction and extreme pressure properties.
The lubricants are tested in accordance with the procedure disclosed in ASTM D3233-73 (Reapproved 1978) using a Falex lubricant tester. The test is performed by applying resistance to a revolvin~ metal journal.
Resistance is applied by two V-Blocks equipped with a ratchet mechanism which steadily increases pressure on the journal. The metal journal and V-Blocks are composed of steel in this example. The metal journal and V-Blocks are submerged in the lubricating composition to be tested.
The results are indicated in the following ~able 1:
Table 1 LUBRICANT
Torque on Journal lbs-in. (Newton-Meters) 450 Neutral Oil with 5 wt.
to-tal of Examples l ana 6 True 450 Neutral Compounds Load Oil ~ No in a Arco ASTM
Lbs.(Newtons) Additives~ atio Graphite SAE 20W/30 300 (1,334)8 (0.904)4 (0.452)6 (0.678)6 (0.678) 500 (2,224,ll (1.243)6 (0.678)8 (0.904)7 (0.791) 750 (3,336)16 (1.808)9 (1.017)16 (1.808)12 (1.356) 1,000 (4,448)Journal14 (1.582)21 (2.373)20 (2.260) Shear 1,250 (5,560) --- 21 (2.373)26 (2.937)24 (2.712) 1,500 (6,672) -~- Journal Journal Journal Shear Shear Shear It should be noted that substantially the same results are obtained when the nickel derivative of Exam~le 7 is substituted for the nickel derivative oE Example 6.

~ -54~
~ra c~ ~7c~ y ,~

.5~

Example 11 The lubricant of Example 10 containing the two compounds of the invention is tested in accordance with the procedure set forth in Example 10 with the following exception: the metal journal and V-Blocks are constructed from cast iron. The results are indicated in the following Table 2:
Table 2 I.UBRICANT
Torque on Journal lbs-in. (Newton-Meters~

450 Neutral Oil with 5 wt.%
total of Examples 1 and 6 True Compounds Load ln a Arco ASTM
Lbs.(Newtons)1:1 ratio Graphite _ SAE 20W/30 300 (1,334) 3 (0.339)6 10.678) 6 (0.678) 500 (2,224) 4 (0.~52~7 (0.791) 7 (0.791) 750 (3,336) 7 (0.791)13 (1.469) 10 (1.130) 1,000 (4,448)12 (1.356)15 (1.6g5) 1~ (1.582) 1,250 (5,560)14 11.582)17 (1.921~ 17 (1.921) 1,500 (6,672)16 (1.808)20 (2.260) 19 (2.146) 1,750 (7,784)18 (2.034)23 (2.599) 21 (2.373) 2,000 (8,896)Journal Wear24 (2.712)Journal Wear 2,250 (10,008) --~ Journal Wear ~-. .
The nickel derivative of Example 7 may conven-iently be substituted for the nickel derivative of Example 6 with substantially the same results.

Example 12 The lubricant of Example 10 containing the two compounds of the invention is tested in accordance with the procedure set forth in Example 10 with the following exception: the journal is constructed from cast iron and the V-Blocks are constructed from chrome. The lubricant properties are comparecl with those of Arco graphite and ASTM, SAE 20W/30 lubricants. The lubricant compositions are tested in accordance with -the procedure disclosed in ASTM:D3233 73 ~Reapproved 1978) using a Falex lubricant tester. The results axe lndicated in the following Table 3:
Table 3 LUBRICANT
Torque on Journal lbs-in. (Newton-Meters) 450 Neutral Oil wi-th 5 wt.%
total of Examples 1 and 6 True Compounds Load in a Arco ASTM
Lbs.(~Jewtons) 1:1 ratio Graphite _ _SAE 20W/30 300 (1,334) 5 (0.565) 4 (0.452) 5 (0.565) 500 (2,224) 6 (0.678) 5 (0.565) 7 (0.791) 750 (3,336) 7 (0.791) 8 (0.904) 10 (1.130) 1,000 (4,448) 12 (1.356) 11 (1.243) 1~ (1.582) 1,250 15,560) 15 (1.695) 16 (1.808) 20 (2.260) 1,500 _(6,672? Journal WearJournal Wear Journal Wear Example 13 An extreme pressure, anti-wear and friction-reducing lubricant composition is prepared by mixing 5weight percent of the zinc additive of Example 8 with 450 neu-tral oil. The lubricant composition reduces wear and frictioIl of metal components in moving contact with each other and~ in addition, lubricates said metal surfaces under extreme pressure or boundary lubrication conditions.

Example 14 The zinc derivative additive of Example 9 is admixed with 450 neutral oil at 5 percent by weight based upon -the total lubricant composition to prepare an extreme ~ 5~tJ~

pressure, anti-wear and friction-reducing lubricant composition. The zinc derivative additive imparts extreme pressure, anti-wear and friction-reducing properties to the 450 neutral, lubricating oil~

Example 15 A lubricant composition containing the nickel heterocyclic compound of Example 6 and 450 neutral oil is tested for extreme pressure, anti-wear and ~riction-reducing properties in a 1973 Chevrolet 350 cu. in. displacement V-8 engine which is run continuously for 196 hours on a single fill of the lubricating composition. The lubrica-ting oil does not contain conventional zinc dialkydithio-phosphate anti-wear additives. The lubricant composition is disclosed in detail in the following Table 4:
Table 4 Weight Percent 450 neutral oil ------~-------------- ------ 89.945 Example 1 Compound ---~ --- 2.500 Mickel Compound of Example 6 ----~ ------- 2.500 Oronite OLOA 12001 ) ------------------~---- 4.000 Chlorowax 40( ) ---------------------------- 1.000 UNAD 242(C) --------------____________ 0.010 Terephthalic Acid( ) ----------------------- 0.025 Quinizarin(E) _____________ _ ______________ 0.020 (A) Oronite OI,OA 1200 - alkyl succinimide type ashless dispersant.
(B) Chlorowax 40 - Chlorinated paraffin containing 40%
chlorine.
(C) UNAD 242 - Silicone type defoamant with kerosene.
(D) Terephthalic acid - Corrosion inhibitor.
(E) Quinizarin - Antioxidant.

~-fad'e ~ J k 5~6~3~

The Chevrolet engine is programmed to run in a repeating cycle that averaged approximately 40 MPEI. The cycle is disclosed in the following Table 5:
Table 5 Cycle RPM Speed MPH (Kilometers/~r.) Time(MIN.) 1 700 0 (0) 2.0 2 1,700 ~5 (72.4) 3.0 3 1,200 30 (48.3~ 4.0

4 2,225 60 (96.5) 0.12 2,400 65 (104 6) 3.0 After the 196 hour engine test is comple-ted, several areas in the engine which are subject to wear are closely examined. These areas include: main bearings, top end bearings, cam shaft bearings, valve lifters and cam shaft lobes.
The length of the engine run is equivalent to approximately 8,000 miles of driving. A detailed examina-tion of the above-described components indicated no abnormal or excessive wear.
Example 16 The extreme pressure, anti-wear and friction-reducing additives of Example 1 and ~xample 2 are individ-ually mixed with SAE lOW/40 mokor oil containing 0.15 weight percent of phosphorus and 0.17 weight percent of zinc. In addition, the motor oil contains 0.21 weight percent of calcium.
The resulting lubricant compositions are tested in accordance with khe procedure disclosed in ASTM D3233-73 (Reapproved 1978) using a Falex lubricant tester. The test, in accordance with the above ASTM designation, is performed by applying resistance to a revolving metal journal. A

rachet mechanism movably attached to two V-blocks applies resistance by steadily increasing pressure on the journal.
The metal journal and ~-blocks (steell are submerged in the lubricant composition to be tested. The results are set forth in the following Table 6:

Table 6 Torque on Journal,lb.-in ~lewtons-Meters?
SAE 10W/40( ) ~AE 10W/40(a) SAE 10W/40(a) True LoadWithout Plus 1 wt.% of Plus 1 wt.~ of lbs (Newtons) Additive Ex.l Compound _ Ex.2 Compound 100 (445)8 (0.904)7 1/2 (0.8~7)7 1/2 (0.847) 250 (1,112) 12 (1.356) 10 (1.130) 9 (1.017) 500 (2,224) 19 (2.147) 15 (1.695) 14 (1.582) 750 (3,336) 22 (2.486~ 18 (2.034) 19 (2.146) 1,000 (4,~481 25 (2.825) 22 (2.486) 22 (2.486) 1,250 (5,560) 35 (3.954) 25 (2.825) 25 (2.~25) 1,500 (6,672) Journal Shear 27 (3.050) 27 (3.050) 1,750 (7,784) ~~ Journal Shear 33 (3.728~
2,250 (10~008) -~ -- Journal Shear ~a) Union Super Motor Oil, marketed commercially by the Union Oil Company of California.
Example 17 A metal heterocyclic compound is prepared by following the procedure of Example 6 with the following changes: 31 grams of reaction product yielded in Example 1 is mixed with 19 grams of lead (II) acetate, 150 ml. of toluene and 25 ml of methanol. The mixture is refluxed for 2 hours, after which, the toluene, methanol, water and acetic acid (produced from acetate) are distilled using conventional techniques and apparatus. The resultlng lead-containing product (32.6 grams) is a golden colored oil with the consistency of honey.
Example 18 ~ he extreme pressure, anti~wear and friction-reducing additive, lead derivative produced in accordance with the procedure of Example 17 is blended with 450 neutral oil at 5 percent by weight based on the total 7 ~

weight of the lubricant composition. The above lubricant composition is compared to Arco graphite lubricant and ASTM hi~h reference oil, SAE 20W-30 for friction reduction and e~treme pressure properties.
The lead derivative and 450 neutral oil mixture is compared to Arco graphite and ASTM, SAE 20W/30 in accordance with the procedure disclosed in ASTM:D3233-73 (Reapproved 1978) using a Falex lubricant tester. The test is performed by applying resistance to a revolving metal journal. Resistance is applied by two V-Blocks equipped with a ratchet mec~anism which steadily increases pressure on the journal. The metal journal and V-Blocks - are composed of steel in this e~ample. The metal journal and V Blocks are submerged in the lubricating composltion to be tested. The results are indicated in the following Table 7:
Table 7 Torque on Journal lbs-in. (Newton-Meters) _ 450 Neutral Oil with True l,oacl Lead Arco ASTM
Lbs.(Newtons~DerivativeGraphite SAE 20W/30 300 (1,334)7 (0.791) 6 (0.678) 6 (0.678) 500 (2,224)11 (1.243) 8 (0.904) 7 (0.791) 750 (3,336)14 (1.582) 16 (1.808) 12 (1.356) 1,000 (~,448)20 (2.260) 21 l2.373) 20 (2.260) 1,250 (5,560)23 (2.599t 26 (2.937) 24 (2.712) 1,500 (6,672)40 (4.520) Journal ShearJournal Shear 1,750 (7,784)85 (9.605) 2,000 (8,896) 94 (10.622) 2,250 (10,000)90 (10.170) 2,500 (11,120)71 (8.023) 2,750 (12,232)79 (8.927) 3,000 (13,344)70 (7.345) 3,250 (~4,456)70 (7.345) __ Stopped due to inabilit~ -to increase load.

~7~ 6 Example 19 A copper-heterocyclic compound is prepared by adding 62 grams of the boron-containing, heterocyclic reaction product yieldecl in Example 1, 150 ml of toluene, 50 ml of water and 18.2 grams of cupric acetate to a 500 ml., single-necked round-bottom flask equipped with a Dean-Stark trap and condenser. The mixture is refluxea for 8 hours, after which, water, toluene and produced acetic acid (from acetate) are disti]led leaving 68 grams of a green solid.

Example 20 The copper derivative additive produced in Example 19 is admixed with 450 neutral oil at 5 weight percent based on the total weight of the lubricant composi-tion and evaluated for performance in accordance with the procedure of Example 18 with the following exception: the lubricant properties of the copper derivative-450 neutral oil mixture are compared with those of 450 neutral oil and SAE lOW/40 lubricants. The results are indicated in the following Table 8:

.~ 5 Table 8 Torque on Journal lbs.-in (Newton-Meters) True Load 450 Neutral Oil 450 Neutral SAE
lbs. (Newtons) with Copper Com- Oil Without 10W - 40 pound from Ex.l9 Additive 300 (1,33~) 9 (1.017) 10 (1.130) 500 (2,224)11 (1.243~ 15 (1.695) 17 (1.921) 750 (3,336)17 (1.921) 23 (2.599) 21 (2.3733 1,000 (4,44~)20 (2.260) Journal28 (3.163) Shear 1,250 t5,560)28 (3.163) 33 (3.728) 1,500 (6,672)55 (6.214) Journal Shear 1,750 (7,784)5S (6.214) 2,000 (8,896)55 (6.214) 2,250 (10,008) 60 (6.779) 2,500 (11,120) 65 (7.345) 2,750 (12,232) 70 (7.909) 3,000 (13,344) 75 (8.474) 3,250 (14,456) 80 (9 038) (Stopped for inspection) Example 21 The boron-containing, heterocyclic compound, 1-hydroxy-3,7-diphenyl-5-coco-5-aza-1-bora-~,8-dioxacyclo-octane, is prepared by adding 14,889 grams of cocoamine(1) and 17,516 grams of styrene oxide to a 65 liter round bottomed flask that contains 13 liters of toluene and 1 liter of water. The flask is placed in a heating mantle and fitted with a water-cooled condenser. The mixture thus formed is heated until it begins to reflux. Next, the temperature is adjusted to give a moderate reflux rate and the reaction mixture is refluxed for 24 hours. The reaction mixture is cooled to room temperature and 4,595 grams of boric acid are added to the flask. Then, the flask is equipped with a Dean-Star]c trap topped with a water-cooled condenser and the reaction mixture is refluxed until water stops collecting in the trap. Toluene is distilled from the reaction product -to an end point at a temperature of ~00 F. (204 C.). The reaction produces ~5~6~

34,373 grams ~f 1-hydroxy-3,7-diphenyl-5-coco-5-aza-1-bora-2,8-dioxacyclooctane.
(1) Cocoamine is a mixture of primary amines consist-ing of approximately 52 percent dodecylamine, 19 percent of tetradecylamine, 9 percent of hexadecyl amine, 6.5 percent of octylamine, 6 percent of decylamine, 2 percent of octadecyl amine and 5 percent of a mixture of octadecenylamine and octadecadienylamine. Cocoamine is produced commercially by the ~rmak Company under the æ~/e ~na, k t~a~=~ of Armeen CD.
.~
Example 22 A boron-containing, heterocyclic compound is prepared by adding 17,605 grams of tallowamine(2) and 15,362 grams of styrene oxide to a 65-liter round-bottomed flask that contains 11.34 liters of toluene and 1 liter of water. The flask is fitted with a water cooled condenser and placed in a heating mantle. The mixture thus formed is refluxed at a moderate rate for 24 hours. The reaction is cooled to room temperature and 4,033 grams of boric acid are added to the flask. Next, the flask is fitted with a Dean-Stark trap, topped with a water-cooled condenser and the reaction mixture is refluxed until water stops collecting in the trap~ Toluene is distilled from the reaction product to an end point temperature of 400 F.
(204 C.). The reaction produces 34,695 grams of l-hydroxy 3,7-diphenyl-5-tallow-5-aza-1-bora-2,8-dioxacyclooctane.

~L~5~

(2) Tallowamine is a mixture of amines consisting of approximately 29 percent hexadecylamine, 20.5 percent octadecylamine, 44 percent of a mixture of octadecenylamine and octadecadienylamine, 3 percent tetradecylamine, 1.5 percent hexadecenylamine, 1 percent heptadecylamine and 0.5 percent tetradecenylamine. Tallowamine is produced commercially by the Armak Company under the tradename Armeen T.

Example 23 l-hydroxy-3,7-diphenyl-5~dodecyl-5-aza-1-bora-2,8-dioxacyclooctane is prepared by adding 13,502 grams of dodecylamine and 17,516 grams of styrene oxide to a 65-liter round-bottomed flask that contains 13.34 liters of toluene and 1 liter of water. The flask is placed in a heating mantle and fitted with a water-cooled condenser.
The mixture thus formed is heated until it begins to reflux. Next, the temperature is adjusted to give a moderate reflux rate and the reaction mixture is refluxed for 24 hours. The reaction mixture is cooled to room temperature and 4,595 grams of boric acid are added to the flask. Then, the flask is equipped with a Dean-Stark trap topped with a water-cooled conclenser and the reaction mixture is refluxed until water stops collecting in the trap. Toluene is distilled from the reaction product to an end-point temperature of 400 F. The reaction produces 32,986 grams of 1-hydroxy-3,7-diphenyl-5-dodecyl-5-aza-1-bora-2,8-dioxacyclooctane.

~57~)t~

E xam~ 4 The compound, l-hydroxy--3,6-dieresyl-5-dodecyl-5-aza-l-bora-2,8-dioxacyclooctane, is prepared by adding 21 grams of boric acid with 61.7 grams of dodecylamine, 89.3 grams of para methylstyrene oxide and 250 ml of toluene to a single necked, one-liter, round-bottomed flask. The toluene acts as a solvent and as an azeotrope for water produced during the reaetion. It should be noted that borie aeid is not soluble in toluene. The flask is plaeed in a heating mantle ancl fitted with a Dean-Stark trap that is topped with a water-eooled condenser. The mixture thus ~ormecl is heated until it begins to reflux. Mext, the mantle heat is adjusted to give a moderate reflux rate.
The reaetion mixture is refluxed for one hour, or until the stoiehiometric amount of water (12 ml) collects in the Dean-Stark trap and all of the boric acid has dissolved, after which the toluene is distilled from the reaction product. The reaction produces 160 grams of product.
Example 25 The compound, 1 hydroxy-3,7--dimethyl-3,7-diphenyl-

5-dodecyl-5-aza-1~bora- 2,8-dioxaeyclooctane, is prepared by followincJ the proeedure of Example 23 with the following substitution:
Alpha methyl styrene oxide is substituted for the styrene oxide with substantially the same results.
Example 26 Boric acid (21 grams), para-tertiary-butyl styrene oxide (119.3 grams~, dodeeylamine t61.7 grams) and 250 ml of toluene are mixed in a one-liter, single-neeked flask ~o prepare 1-hydroxy-3,7-para-tertlary-butylphenyl-5-dodecyl-5-aza-1-bora-2,8-dioxacyclooctane. The flask is equipped with a heating mantle, Dean~Stark trap and water cooled condenser. The mixture is heated under reflux until the reaction is completed; 12 ml of water collects in the Dean-~tark trap. Next, toluene is distilled from the reaction mixture. The product thus prepared is suitable for use as an extreme pressure, anti-wear and friction-reducing additive for lubricating compositions.
It should be noted that the other primary amines herein may be substituted for the dodecylamine above, to form the corresponding boron heterocyclic compound.

Example 27 A copper derivative of l-hydroxy-3,7~diphenyl-5-coco 5-aza-1-bora-2,8-dioxacyclooctane is prepared by following the procedure Example 21 with the following exception: the above-described compound (47 grams), 100 ml of toluene, 20 ml of triethyl amine and 10 grams of cupric acetate are mixed in a single-necked, 500 ml round-bot-tomed flask, equipped with a heating ~lantle and water-cooled condenser. The mixture is refluxed for 16 hours, then filtered and the toluene, amine, water and acetic acid (produced in situ) are distilled from the re~ction product. Using the above-procedure, copper di-[l-oxy-3,7-diphenyl-5-coco-5-aza--1-bora-2,8-dioxacyclooctane] is produced.

~57606 Example 28 ~ nickel derivative of 1-hydroxy-3,7-diphenyl--5-coco-5-aza-1-bora-2,8-dioxacyclooctane is prepared by following the procedure of Example 27 with the following exception:
An equivalent amount of nickel acetate is substituted for the cupric acetate. The reaction produces nickel cli-[1-oxy-3,7-diphenyl-5-coco-5-aza-1-bora-2,8-dioxacyclooctane].

Example 29 Lead di-[1-oxy-3,7-diphenyl-5-coco-5-aza-1-bora-2,8-dioxacyclooctane] is prepared in accordance with the procedure of Example 21 with the following exception:
The reaction product produced in Example 21 (23.5 grams), 100 ml of toluene, 9.5 grams of lead acetate and 10 ml of triethylamine are mixed in a single-necked 500 ml round bottomed flask, equipped with a water-cooled condenser and heating mantle. The mantle heat is adjusted until a moderate rate of reflux is obtained. The mixture thus formed is refluxed for 18 hours. Next, the mixture is filtered, and toluene, water, triethylamine and acetic acid (produced in the reaction) are distilled from the reaction product. The reaction produces lead di-[1-oxy-3,7-diphenyl-5-coco-5-aza~1-bora-2,8-dioxacyclooctane.

Example 30 Iron di-(1-oxy-3,7-diphenyl-5-coco-5-aza-1-bora-2, 8-dioxacyclooctane) is prepared according to the procedure of Example 21 with the following exception~

~57~

A mixture comprisin~ 23.5 ~rams of the reaction product produced in Example 21, 100 ml of toluene, 4.3 grams of ferrous acetate and 10 ml of triethylamine are introduced into a single-necked, 500-ml, round-bottomed flask, equipped with a water-cooled condenser and heating mantle and Dean-Stark trap.

Example 31 A boron compound of the invention is prepared by adding 17,093 grams of octadecylamine and 15,362 grams of styrene oxide to a 65-liter, round-bottomed flask that contains 13 liters of -toluene and 1 liter of water. The flask is fitted with a water-cooled condenser and placed in a heating mantle. The mixture thus formed is refluxed at a moderate rate for 24 hours. The reaction is cooled to room temperature and 4,033 grams of boric acid are added to the flask. Next, the flask is fitted with a Dean-Stark trap, topped with a water-cooled condenser and the reaction mixture is refluxed until water stops collecting in the trap. Toluene is distilled from the reaction product to an end-point temperature of 400 F.
The reaction produces 34,183 grams of 1-hydroxy-3,7-diphenyl-5-octadecyl-5-aza-1-bora-2,8-dioxacyclooctane.

Example 32 The procedure of Example 31 is followed to ~roduce l-hydroxy-3,7-diphenyl-5-phenyl-5-aza-1 bora-2,8-dioxacyclooctane with the following exception:
An e~uivalent amoun-t of phenylamine is substi-tuted for octadecylamine.

o~-i Example 33 ~ inc di-[l-oxy-3,7-diphenyl 5-coco-5-aza-1 bora-2,8-dioxacyclooctane] is produced according to the proce-dure of Example 27 except that an equivalent amount of zinc acetate is substituted for the cupric acetate.

Example 34 Tin di-[l-oxy-3,7 diphenyl-5-coco-5-aza-1-bora-2,8-dioxacyclooctane] is prepared by substituting an equivalent amount of tin acetate for the cupric acetate in Example 27.

Example 35 Lead di-[l-oxy-3,7-diphenyl-5-dodecyl-5-aza-1-bora-2,8-clioxacyclooctane] is prepared in accordance with the procedure of Example 23 with the following exception:
The reaction product produced in Example 23 (23.95 grams), 100 ml of toluene, 9.5 grams of lead acetate, and 10 ml of triethylamine are mixed in a single-necked, 500-ml, round-bottom flask, equipped with a water-cooled condenser, heating mantle and Dean-Stark trap. The mantle heat is adjusted until a moderate rate of reflux is obtained. The mixture thus formed is refluxed for 18 hours. Next, the mixture is filtered and the toluene, triethylamine, water and acetic acid (produced in-situ) are distilled from the reaction product. The reaction produces lead di[-l-oxy-3,7-diphenyl-5-dodecyl-5-aza-1-bora-2,8-dioxacyclooctane].

)6 Example 36 A nickel derivative of l-hydroxy-3,7-dicresyl-5-dodecyl-5-aæa-1-bora-2,8-dioxacyclooctane is prepared by following the procedure of Example 35 with the following exception:
~ n equivalent amount of paramethyl styrene oxide is substituted for styrene oxide and niekel acetate is substituted for lead acetate. The reaction produces niekel di[-1-oxy-3,7 dicresyl 5-dodeeyl-5-a2a-l-bora-2,8-dioxacyclooctane].

Example 37 Iron di-[l-oxy-3,7-di-para-tertiary-butyl-phenyl-5-dodecyl-5-aæa-1-bora-2,8-dioxacyclooetane] is prepared according to the procedure of Example 26 with the following exception:
A mixture eomprising 28.4 grams of the reaction produet produced in Example 26, 100 ml of toluene, 4.3 grams of ferrous acetate and 10 ml of triethylamine are introdueed into a single-neeked, 500~ml, round-bottom flask, equipped with a Dean-Stark trap, water-eooled eondenser and heating mantle. The heating mantle is adjusted to give a moderate rate of reflux of the reaetion mixture. The mixture is refluxed for 18 hours, filtered, and the toluene, triethyl-amine, water and aeetic acid (produced in-situ) are distilled from the reactlon product.

~57~0~j Example 38 Zinc di~ oxy-3,7-diphenyl-5-dodecyl-5-aza-1-bora-2,8-dioxacyclooctanel is produced according to the procedure of Example 35 except that zinc acetate is substituted ~or lead acetate.

Example 39 Tin di-[1-oxy-3 t 7-diphenyl-5-dodecyl-5-aza-1-bora-2,8-dioxacyclooctane] is prepared by substituting tin acetate for lead acetate in Example 35.

Examples 40 to 46 Extreme pressure, anti-wear and friction-reducing additives produced according to the procedure of Examples 21, 27, 29, 30, 33 and 34 are mixed with separate portions of 450 neutral oil at concentrations of 2 weight percent.
Each lubricant composition is tested in accordance with the procedure disclosed in ASTM:D3233-73 (Reapproved 1978) using a Falex lubricant tester. The test, in accordance with the above ASTM designation, is performed by applying resistance to a revolving metal journal. A
rachet mechanism movably attached to two V blocks applies resistance by steadily increasing pressure on the journal.
The me-tal journal and V-blocks (steel) are submerged .in the lubricant composition to be tested. A summary of the results obtained is disclosed in the following Table 9:

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Examples 47 and ~8 The extreme pressure, anti-wear and friction-reducing additive produced in accordance with the pxocedure of Example 21 is mixed at a concentration oE 2 weight percent with SAE 30 motor oil which contains 0~05 weight percent phosphorus. A sample of the SAE 30 motor oil which does not contain the additive of Example 21 is used as a control. This control was blended 6.5 volume percent (7.05 weight percent) Amoco PCO-059 in ~nion 450 neutral.
(See footnote (E~ in Table 12 hereafter.) Each lubricant composition is tested in accord-ance with the procedure disclosed in ASTM D3233-73 (Reap-proved 1978) using a Falex lubricant tester. A su~nary of the results in disclosed in the following Table 10:
Table 10 Torque on Journal lbs.-in (Newton-Meters?
Example 47 48 True ~oad Control (SAE 30SAE 30 Motor Oil lbs. (Newtons)Motor Oil)with Additive of Ex.21 300 (1,33~)9 (1.017~ 8 (0.904) 20500 (2,224)14 (1.5~2)12 (1.356) 750 (3,336)20 (2.260~17 (1.921) 950 (4,404)Journal Shear ---1,000 (4,448) --- 22 (2.486) 1,250 (5,560) --- 28 (3.163) 1,400 (6,227) --- Journal Shear The extreme pressure property of SAE 30 motor oil is substantially enhanced in Table 10 above when 2 weight percent of l-hydroxy-3,7-diphenyl-5-coco-5-aza-1-bora-2,8-dioxacyclooctane is added to said SAE 30 motor oil.

~73---fr~ ~ c, r~

o~

Example 49 A copper corrosion inhibltor comprising 1,3,4-thiadiazole-2,5-bis(dodecyldisulfide) is prepared by chlorinating 284 grams of n-dodecyl mercaptan in 0.6 liter of carbon tetrachloride with 1.47 moles of chlorine over a two-hour period at a temperature of about 23 F. (-5 C.) to about 32 F. (0 C.). ~ext, sulfenyl chloride which forms as a reaction product is stripped with nitrogen to remove hydrogen chloride, and the resultant compound is added to 86 grams of a 2,5-dimercapto-1,3,4-thiadiazole slurry. The mixture is heated at 86 F. (30~ C.) for 1 and 1/2 hours and the resultant compound (1,3,4-thia-diazole-2,5-bis(dodecyldisulfide) is recovered by washing with water and sodium bicarbonate and vacuum stripping to remove carbon tetrachloride.

Example 50 The procedure of Example 49 is followed to prepare 1,3,4-thiadiazole-2,5-bis (octyldisulfide) with the following exception: octyl mercaptan is substituted for the dodecylmercaptan.

Example 51 The oxidation inhibitor, thiodiethyl bis-(3,5-di-t-butyl-4-hydroxy) hydrocinnamate, is prepared by melting together 17.95 weight percent of beta,beta'~dihydroxy-diethyl sulfide, 81.41 weight percent of (3,5-di~t~butyl-4-hydroxy) hydrocinnamate acid and 0.64 weight percent of sodium methylate under a nitrogen atmostphere at 266 E~.
(130 C.) for two and one-half hours. Methanol thus 6Q~i formed is separated from the reaction mixture and condensed in a dry-ice -trap using nitrogen gas as a carrier. The reactants are heated at 149 F. (65 C.) for three hours and the reaction product is dissolved in warm benzene, filtered and the benzene filtrate is washed three times with sa-turated sodium chloride solution. The filtrate is, next, dried over anhydrous sodium sulfate and the solvent evaporated using conventional techniques. Thiodiethyl bis~(3,5-di-t-butyl-4-hydroxy) hydrocinnamate is isolated and purified by successive recrystallization from hexane and a mixture of hexane and t-butanol.

Example 52 The oxidation inhibitor, bis(dithioben~il) iron (II), is prepared by adding 400 grams of ben~oin and 600 grams of phosphorous sulfide to a single-necked, 5-liter, round-bottomed flask equipped with heating mantle and water-cooled condenser and containing 1,500 ml of dioxane.
The mixture thus formed is refluxed for two hours. Next, 20 200 grams of hydrated ferrous chloride dissolved in 500 ml of water is added to the 5 liter flask and the mixture is heated on a steam bath at 212 F. (100 C.) for 2 hours.
The reaction product thus formed (169.5 grams) is filtered and washed with methanol.

~ample 53 Dodecylamino di~phenylethylate) hydrogen borate is prepared by adding 34.85 pounds (15,808 grams) of dodecylamine (1 e~uivalent) and 41.0 pounds (18,597 grams) 30 of styrene oxide (2 equivalents) to a 17 U.S. gallon (64.3 ~5~ 6 liters~ round bottomed flask equipped with a water-cooled condenser and containing 3 U.S. gallons (11.36 liters3 toluene and 1 liter o~ water. The reaction is exothermic and begins immediately upon addition of the above reactants. Additional heat is applied and the reaction mixture is refluxed for a total o~ 24 hours; however, as little as 2 hours may result in complete reaction. The reaction is cooled -to room temperature, 10.49 pounds (4,758.16 yrams) of boric acid (1 equivalent) is added and the flask is equipped with a Dean-Stark trap. Heat is again applied and -the reaction mixture refluxed until water stops collecting in the trap. Toluene is, then, distilled from the reaction product at a temperature of 400 F. (204 C.) or less. About 6 liters of water collect in the Dean-Stark trap. The reaction produces approximately 75 pounds (34,019 grams) of product.

Examples 54 to 60 ~ lubricant composition containing dodecylamino di(phenylethylate) hydrogen borate, 1,3,-4-thiodiazole-2,5-bis(octyldisulfide), terephthalic acid, and thiodiethyl bis-(3,5-di-t-butyl-~-hydroxy) hydrocinnamate is tested for copper and lead corrosion inhibition and anti~oxidant properties using a single-cylinder Labeco CLR Test Engine equipped with sintered copper (65 wt.%)/lead (35 wt.%) connecting rod bearings, in accordance with the procedure of Federal Test Method Standard ~o. 791B, method 3405.2.
The same lubricant composition, but containing bis(dithio--benzil)irontII) substituted for the hydrocinnamate compound, is also tested by the same procedure.

~5~

The copper-lead corrosion tests are conducte~ in accordance with the test conditions of the following Table 1 1 :
Table 11 Operating Conditions Test Duration, Hours 40 Speed, RPM 3150 + 25 Load, BHP 6.5a (KW) (4.85) Fuel, Flow, Lb/Hr. 4.75 + 0.25 (gm/Hr.) (2,155 + 53 Air/Fuel Ratio 14.0 + 0.5 Jacket Outlet Coolant Temp.,F. 200 + 2 (C.) (93.33 -~ 1.113 Gallery Oil Temp., F. 290 + 2 IC.)(143.33 ~ loll~
Spark Advance, BTDC 35 + 1 Oil Pressure, PSIG 40 + 2 (atmospheres) (3~72) Crankcase Vacuum, in. H O2 + 0.5 (cm. ~2) (5.08 ~ 1.27) Exhaust Back Pressure, in. Hg. 0.5 ~ 0.5 (cm. Hg) (1.27 + 1.27) Crankcase Off-Gas, CFH 30 + 1 tCMH)(0.83 ~ .03) Oil Charge, Pints 3.5 (Liters) (1.66~
The test is conducted by charging 3.5 pints (1.66 liters) of the test lubricant to the engine sump.

Test duration eonsists of 40 hours operation at the prescribed test conditions of Table 11 above. When the prescribed gallery oil temperature is reached, the test time begins. Interim oil acljustments are made at the end of 10, 20 and 30 hours of test operation. A copper/lead bearing weight loss (BWL) of about 40 mg of lower is considered acceptable. All of the tests are eonducted on blends based upon the control using SAE 30 motor oil further containing the additives and/or compouncls, at the concentrations in the following Table 12:

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~ ~' Lt~ ~D ~ ~ ~ O ,_ ~ ~ _ _ _ ~ ~ Ln n n r 5i 7 ~ 6 Example 61 The bis(hydrocarbyloxy methylated) boron-containing heterocyclic compound, 1-hydroxy-3,7-di(methyl phenoxy methyl)-5-coco-5-aza-1-bora-2,8-dioxacyclooctane r is prepared by adding 278.5 grams of cocoamine and 450.5 grams of cresyl glycidyl ether to a 2-liter round-bottomed flas]c that contains 250 ml of toluene and 22 ml of water.
The flask is placed in a heating mantle and fitted with a water-cooled condenser. The mixture thus formed is heated until it begins to reflux. Next, the temperature is adjusted to give a moderate reflux rate and the reaction mixture is refluxed for 18 hours. The reaction mixture is cooled to room temperature and 86.0 grams of boric acid are added to the flask. Then, the flask is placed in a heating mantle and fitted with a water-cooled condenser.
The mixture thus formed is heated until it begins to reflux. Next, the temperature is adjusted to give a moderate reflux rate and the reaction mixture is refluxed for 18 hours. The reaction mixture is cooled to room temperature and 86.0 grams of boric acid are added to the flask. Then the flask is equipped with a Dean-Stark trap topped with a water-cooled condenser and the reaction mixture is refluxed until water stops collecting in the trap. Toluene is distilled from the reaction product to an end-point temperature of 400 F. (20~ C.). The reaction produces 758.5 yrams of 1-hydroxy-3,7-di(methyl-phenoxymethyl)-5-coco-5-aza-1-bora-2,8-dioxacyclooctane.

5~7~

Exam~le_62 The bis(hydroxycarbyloxymethylated) boron-containing, heterocyclic compound, 1-hydroxy-3,7-di(methyl-phenoxymethyl~-5-oleyl-5-aza 1-bora-2,8-dioxacyclooctane, is prepared by adding 55.6 grams of oleyl amine and 66.0 grams of cresyl glycidyl ether to a 1 liter round-bottomed flask that contains 250 ml of toluene. The flask is placed in a heating mantle and fitted with a water~cooled condenser. The mixture thus formed is heated until it begins to reflux. Next, the temperature is adjusted to give a moderate reflux rate and the reaction mixture is refluxed for 18 hours. The reaction mixture is cooled to room temperature and 12.~ grams of boric acid are added to the flask. Then, the flask is equipped with a Dean-Stark trap topped with a water-cooled condenser and the reaction mixture is refluxed until water stops collecting in the trap. Toluene is distilled from the reaction product to an end point temperature of 400 F. (20~ C.). The reaction produces 97 grams of 1-hydroxy-3,7-di (methyl-20 phenoxymethyl)-5 oleyl-5-aza-1-bora-2,8-dioxacyclooctane.

~xample 63 The compound, 1-hydroxy-3,7-di(methyl phenoxy methyl)-5-dodecyl-5 aza-1-bora 2,8-dioxacyclooctane, is prepared in accordance with the procedure of Example 61 with the following exception: one mole of dodecylamine is substituted for each mole of cocoamine used.

1~5~ 3~i Example 64 The compound, l-hydroxy-3,7-di(methyl phenoxy methyl)-5-tallow-5-aza-1-bora-2,8-dioxacyclooctane, is prepared in accordance with the procedure of Example 62 with the following exception: one mole of tallowamine i5 substituted for each mole of oleyl amine used.

Example 65 A copper derivative of l-hydroxy-3,7-di(methyl 10 phenoxy methyl)-5-coco-5-aza-1-bora-2,8-dioxacyclooctane is prepared by following the procedure of Example 61 with the following exception: the compound of Example 61 147 grams), 100 ml of toluene, 20 ml of triethyl amine and 10 grams of cupric acetate are mixed in a single-necked, 500 ml round bottom flask, equipped with a heating mantle, Dean-Stark trap and water-cooled condenser. The mixture is refluxed for 16 hours, then filtered and the toluene, amine, water and acetic acid (produced in situ) are distilled from the reaction product. Using the above procedure, copper di[l-oxy-3,7-di(methyl phenoxy methyl)-5-coco-5-aza-1 bora-2,8-dioxacyclooctane] is produced.

Examples 66 to 71 The compound l-hydroxy-3,7-di-(methylphenoxy-methyl)-5-coco-5-aza-1-bora-2,8-dioxacyclooctane produced in accordance with the procedure of Example 61 is tested for extreme pressure, anti-wear and friction-reducing properties admixed with separate portions of 450 neutral oil and SAE 30 motor at concentrations of 1 and 2 weight percent respectively. Samples of 450 neutral oil and the ~81-control SAE 30 motor oil [Example 47) without the compound 1-hydroxy-3,7~di-(methylphenoxymethyl)-5-coco~5-aza-1-bora-2,8-dioxacyclooctane serve as controls of the experi-ments.
Each lubricant composition is tested in accord-ance with the procedure disclosed in ASTM:D3233-73 (Reap-proved 1978) using a Falex lubricant tester. The test, in accordance with the above ASTM designation, is performed by applying resistance to a revolving metal journal. A
rachet mechanism movably attached to two V-blocks applies resistance by steadily increasing pressure on -the journal.
The metal journal and V-blocks(steel) are submerged in the lubricant composition to be tested. A summary of the results obtained is disclosed in the following Table 13:

-8~-' tj~t ~ ,~ o~o ~ o ~ ~ ~9 r~
r~ r~ v r~ J~ r~ ~ N C;~
O ~ ~ ~ ~ N

~ r~ r~ N

10 1~'~ 3 r~ ~r r~) ~ r~l r~~ ~_ r~ ~ O 7 F ~ o\o r-~ ~D ro r~l ~3 ~i r~ æ ~ r~ i o o u~ ~ ~o 1~ r~
2 o ~ . rJ ~ r~
G .,; ~ ~

~O ~; O r-i ~ l~
r r r rt~ r~l ~D ~ u) ~ cn ~o r r7 r~ ~o r~ In r r u~ ~D
a) ~ 1 ~ ~ o }~
o o o u~ o o o r o r o ~ r~

~ 3~

As shown in Table 13, the addition of 1-hydroxy-3, 7-di-(methylphenoxymethyl)-5-coco-5-aza-1-bora-2,8-dioxa-cyclooctane to 450 neutral oil and to the control SAE 30 motor oil (Example 473 at concentrations of one and two weight percent, respectively, imparts extreme pressure properties to the oils~

Example 72 A lubricant composition is tested for copper and lead corrosion inhibi-tion properties using a single-cylindered Labeco CLR Test Engine equipped with sintered copper (65 wt.~)/lead (35 wt.~) connec-ting rod bearings, in accordance with the procedure of Federal Test Method Standard No. 791B, Method 3405.2.
The test is conducted in accordance with the test conditions of Table 11 in previous Examples 54 to 60.
In additionl the test is conducted by charging 3.5 pints (1.7 liters) of the test lubricant to the engine sump. Test duration consists of 40 hours operation at the prescribed test conditions of Table 11 above. When the prescribed gallery oil temperature is reached, the test time begins. Interim oil adjustments are made at the end of 10, 20 and 30 hours of test operation. A copper/lead hearing weight loss (BWL) of about 40 mg or lower is considered acceptable.
The lubricant composition tested in this Example 72 is a standard 450 neutral oil containing the additives and concentrations shown in Tab]e 14. Also shown in Table 14 is the result of the experiment.

J~

8 ~ ~

ô o o, ~ o ~ o U~ ,~ ~ ~ ~` 52 ~ ~
_ -U ~ $
~L~
o ~
co ~ ~ O ,~a .~ U

'~ ~ ~ ~
~ o ~
E-l ~ ~ . N ,C ~ O
~- I o I ~ 0 ~
O ~1 0 ~~
0~ I ~ ~40 O m^ ,~
2 0 ~ h ~`P u~
O O ~ r~ a) ~
o E~ ~ 0 ~ H o ~ ~, O

O -~ ~ -- H ~) ' ;~ -~
~r~ o~O ~. ~ 0~
~1 ~- ~ O~-o ~ ~ ~
~ UO 11 ~1 ~ ~
~1 ` ~ â:~ v c ~

~5-~7~ 6 Example 73 A lubricant composition containing 450 neutral oil, l-hydroxy-3,7-diphenyl-5-coco~5-aza-1-bora-2,8-dioxa-cyclooctane, and octyl diphenyl amine is tested for extreme pressure properties, and resistance to oxidation stability, and corrosion using a single cylinder Labeco CLR Test Engine equipped with sintered copper (65 wt.~)/
lead (35 wt.%) connecting rod bearings, ln accordance with the procedure ASTM STP 509A, Part IV and the engine 10 operating conditions of Examples 54 to 60 and 72. The total phosphorus content was 0.075 weight percent.
The results are summarized in the following Table 15:

~L;2t~

.~
~1 ~ . -~

_ _ ~ ~1 ~ ~ ~
~ I ~
cA ~
' o ~ ' _ ~ U ~1 ~ ¦ ~ ~ u ,1~
d~ ~ $ ~ ~ ~
U 3 o o ,1 h L~ U
~ o $ ,~ ,~ o OU a~ ~ ~

2 0~ o ,~
I ,~ ~ h ~_ ~ 4~
Il ~ o~ LO
-~... o ~ ~ ~ o ~ ~ ~ 8 ~; ~ 3 ~ h ~ o ~ ~ ~ 8 ~ N LO ~
r~J .~ ~ U ~ 1I h O h 1~ ~ ~ 11 ~ 'g ~
r~
~ ~ -- ~ ~ ~ ~
~ ~ ~ u ~L~5~

Example 74 The lubricant composition disclosed in Table 15 of E~ample 73 is tested in a 1977 Oldsmobile~ -8 engine - for 64 hours in accordance with the following 1977 General Motors Lubricant Evaluation Sequence III D test.
Prior to each test run, the engine is completely disassembled, solvent cleaned, measured and rebuilt in strict accordance to furnished speciEications. Following the preparation, the engine is installed on a dynamometer test stand equipped with the appropriate accessories for controlliny speed, load, temperatures and other various engine operating conditions.
The engine is operated on a 4-hour break-in-schedule aEter which oil is sampled and leveled. The engine is then operated under non-cyclic, moderately high speed, high load and temperature conditions for a test duration of 64 hours, with oil leveling and oil additions each 8 hours.
In the following Table 16 is a summary of these operating conditions:

fr~de ~n~7~

~L ~ r~

Table 16 Speed, rpm 3000 + 20 Load, bhp 100 t 2 (Kw) l74.6 + 1.49) Oil, to engine, after filter, F. 300 + 2 (C.) ~149 + 1.1) Oil pump outlet, psig min 40 (atmospheres min) (3.72) Coolant, jacket out, F. 245 + 1 (C.)(18.3 + 0.6) jacket in, F. 235 -~ 1 (C.)(112.8 + 0.6) jacket flow rate, gpm 60 ~ 1 (lpm) (227 + 3.8) rocket cover out, F. 240 + 3 (C.) (115.56 ~ 1.67) at gpm per cover at 1.5 + 0.5 (lpm~ (5.7 + 1.9) breather tube out, F. 100 + 2 (C.) (37.8 + 1.1) at gpm at 3.0 + 0.5 (lpm) (11.36 + 1.9) Air-fuel ratio 16.5 -~ 0.5 Caxburetor, air temperature ,F. 80 t 2 (C.) (26.7 ~ 1.1) Carburetor, air humidity, grains per lb of dry air80 + 5 (grams per gram of dry air~ (0.01143 ~ 0.0007) Carburetor, pressure, in. of water 0.1 to 0.3 (cm)(.3 to .8) Blowby rate, cfm at 100F. and 29.7 in. 2.0 + 0.3 (37.78 C.) and (75.4 cm) of ~y (0.0566 + 0.0085) Intake manifold vacuum, in. of ~Ig 7 ~ 2 (cm)(17.78 + 5.08) Exhaust back pressure, in. of water 30 + 2 (cm)(76.2 + 5.08) Exhaust back pressure, max differential, in.(cm) of water 0.2 (0.51) After every 8 hours of testing, a 25-minute shutdown period is provided for oil sampling, additions and level adjustments. The total running test time for Sequence IIID is 64 hours. The results are su~mari~ed in the following Table 17:

C~

Table 17 Test Result ~PI "SF" Limit (A) Engine Sludge Rating ~10=clean) 9~ 9.2 min.
(B) Piston Varnish (10=clean) 9.4 9.2 min.
(C) Cam & Lifter Wear (inch) 0.0019 0.0080 max.
(D) 64 hour Viscosity increase, ~ 1~2 375 max.
(E) Oil Consumption, quarts 3.06 6.38 max.
The engine tests are performed in accordance with the Coordinating Research Council (CRC) rating and techniques located in CRC Manual NOS 9 and 12.

Example 75 A sul~urized, boron-containlng, heterocyclic compound is prepared by mixing 12 yrams of oleylamine, 9~6 grams of styrene oxide and 200 ml of toluene for 30 minutes at room temperature (25 C.) in a single-necked one-liter round-bottomed flask. The flask is placed in a heating mantle and equipped with a water-cooled condenser.
The mixture is heated under reflux for three hours produc-ing an oleylamine/styrene oxide adduct.
The adduct is cooled to room temperature and 2O~7 grams of boric acid is added to the flask. Next, the resulting mixture is refluxed until 1.4~ ml of water collects in an added Dean-Stark trap. rrhe Elask and contents are moved to a rotary evaporator where toluene is stripped from the boron-containing, heterocyclic compound (18 grams).
Sulfur (0.96 grams) and 75 ml of toluene are added to the round-bottomed flask and the resulting mixture i9 heated to reflux temperature with mixing for four hours, after which the toluene is distilled off under vacuum, to yield the desired reaction product.

Example 76 The reaction product of Example 75 is tested for extreme pressure properties in 450 neutral oil in accord-ance with the procedure disclosed in ASTM:D 32 33-73 (Reapproved 19781 using a Falex lubricant tester. The test is performed by applying resistance to a revolving metal journal. A rachet mechanism movably attached to two V-blocks applies resistance by steadily increasing pressure on the journal. The metal journal and V-blocks (steel) are submerged in the lubricant composition to be tested.
The results are summarized in the following Table 18:
Table 18 Torque on Journal lb.-in.(Newtons-Meters) 450 Neutral Oil (A) True Load 450 Neutral Oil (A) with 2.25 wt.
lbs.(Newtons)without additive additive -300 (1,334) 9 (1.017) 2 (0.226) 500 (2,224) 12 (1.356) 4 (0.452) 750 (3,336) xx 8 (0.904) 1,000 ~4,448) 13 (1.469) 1,250 (5,560~ 18 (2.034) 1,500 (6,672) 23 (2.599) l,750 (7,784) xx (A) 450 Neutral Oil, marketed commercially by Union Oil Company of California.

Example 77 A sulfochlorinated, boron-containing, hetero-cyclic compound is produced by adding 20 grams of l-hydroxy-3,7-diphenyl-5-oleyl-5-aza-1-bora-2,8-dioxacyclooctane, 10 ml of toluene and 1.76 grams of sulfur monochloride to a one liter round-bottomed flask equipped with heating mantle and water- cooled condenser. The mixture thus formed is heated at 200 F. (93.33 C.) for 45 minutes, 30 then 6.3 grams of 450 neutral oil is added to the flask and the toluene evaporated. The compound 10,10'-dithio-di[9-chloro-1-(5-hydroxy-3,7-diphenyl-1-aza-4,6-dlocta-5-bora-cyclooctyl)-octadecane] is produced in this reaction.

Example 78 The compound dithiodi-[1-(5-hydroxy-3,7-diphenyl-1-aza-4,6 diocta-5-bora-cyclooctyl)-chlorotallow] is produced in accordance with the procedure of Example 75 with the following exception:
20 grams of 1-hydroxy-3,7-diphenyl-5-tallow 5~
aza~1-bora-2,8-dioxacyclooctane and 1.215 grams of sulfur monochloride are added to the one liter round-bottomed flask.

Examples 79 to 81 The compounds produced in Examples 77 and 78 are tested for extreme pressure properties by admixing each compound with separate portions of 450 neutral oil at concentrations of 2 weight percent. A sample of ~50 neutral oil without an additive (compound) serves as a control in the experiment.
Each lubricant composition is testecl in accord-ance with the procedure disclosed in ASTM:D 32 33-73 (Reapproved 1978) using a Falex lubricant tester contain-ing a steel journal and V-blocks. A summary of the results obtained dlsclosed in the following Table 19:

7~0~

r~
rl rr v r~
,~ ~o ~ co o ~ ~r ~ ~ ~ r~ r~ c~ ~ I` ~ ~
r~ h d~ ~ ~ o ~ u~ 1--CO Z O O ~ r~ ~ ~ ~ _ ~
~ 11-1 e:r ~O o e;l~ CC\ r-l('~) ~
U~,~ ~ l ~) _ ~ r~'~
rl r U~
r~ I~
~:1 ~ ~ ~r~) o Z h ~P ~ ~o ~~r ~r x _ O ~ ~) X O OOr~lr--l r1 r-l ~ r~
i~ ~ l _ _ _ _ _ _ _ 1 ~H ~ ~ 0~ ~ ~ ~ ~ b~
~11 ~ O O r-~r~
~ ~ ~.~ .~

ZV .1_~
~ v 2 0 ~cn ~ ~ ~i ~r .~1 ~ $
u~ ~ D CO O ~ ~' ~ o 'r~
~ ~ ~ ~ ~t' ~ I~ 0~ ~ O
rl l ~3 ~ ~ ~ ~r n ~ ~ ~ O ., ~ 3 r-l t~ x '~1 '~ ~ -- ---- -- -- -- -- -- _ X
~ O g Ln O Ln O Ln O Ln ~ Q ~) ~ ~ O ~I Lnt-- O t` J r li ~ i--1 r-~ r-lr-l r~ l ~93~

~r~7~

Example 82 A chlorinated, boron-containing, heterocyclic eompound is prepared by placing 71.3 grams of A mixture eontaining 75 weight pereent of 1-hydroxy-3,7-diphenyl-5-tallow-5-aza-1-bora-2,8-dioxaeyelooctane and 25 weight pereent o~ 450 neutral oil into a 250 ml Pyrex ~lask equipped with a side arm. Chlorine gas is introduced into the flask through a Tygon tube attaehed to a glass tube equipped with a rubber stopper and extending to the bottom of the flask. The chlorine gas is bubbled through the heterocyelic compound with ayitation. Excess c3as is vented through the side arm of the flask, Tygon tubing and glass tubing into an aqueous solution of 10% potassium hyciroxide. The ehlorine gas was bubbled through the system for 15 minutes giving a total weight gain of 3.2 grams to the heterocyelie eompound. The eompound thus produced is l-hydroxy~3,7-diphenyl-5-(perehlorotallow3-1-bora-2,8-dioxa-5-aza~cyclooctane.
~xample 83 A brominated, boron-containing, heterocyclic compound is prepared by plaeing 71.33 grams of a mixture containing 75 weight percent of 1-hydroxy-3,7-diphenyl-5-tallow-5-aza-1-bora-2,8-dioxacyclooctane and 25 weight percent of 450 neutral oil into a 250 ml Pyrex flask equipped with a heating mantle and thermometer.
Liquid bromine (6.37 grams) is added to the Pyrex flask and the mixture is agitated for ten minutes.
Next the mixture is heated at 120~ F. (49 C.) for ten minutes. The eompound l-hydroxy-3,7-diphenyl-5-(perbromo-tallow)-1-bora-2,8-dioxa-5-aza-eyclooctane is produced.

C

Example 8~ to 88 The compounds produced in Examples 82 and 83 are tested for extreme pressure properties by admixing each compound with separate portions of SAE 30 motor oil contain-ing 0.05 weight percent phosphorus (added as zinc dialkyl-dithiophosphate) and the concentration of additive indicated in Table 20 below. A sample of the control SAE 30 motor oil (Example 47) without an additive (borate of the present invention) serves as a control in the experiment.
Each lubricant composition is tested in accord-ance with the procedure disclosed in ASTM:D 32 33-73 (Reapproved 1978) using a Falex lubricant tester contain-ing a steel journal and V-blocks. A summary of results obiained is disclosed in the following Table 20:

~ oP
r~ ~ _ _ ~ _ _ .
~ L~ 1~ O LO O ~
CD ~1 _ ~ ~ ~ 7 1 ~ 7 . I ~ .L.
CD Ei ~ o o r I I ~ 1 ~ 00 ~t) CO N ~ Q .~
~ _ ~U~
r~ ~oP ~ ~ O N C~ ~ .~
~ O ~r ~D r--I CO S~l I r -IJ
~_ rd ~ (`~I N ~ I
1-- ~H -- O r; ~ N I ~ ~ 7 ~) ,p i: lGO ~ O ~ a IJ N l l l r~
.~ 00 CO r--l O ~ O
r-l ~j !~ .,~ oo i~,~
O ~ .~ _ _ _ _ '~ ~
lrT~ r-~ LD ~ N ~1rl r--i P IL9 ~ ~I r--~ O ~ N ~ 7 i I ~ ~
~Q ~_i CO Or--l r-l N I I N a) I I i ~) ~
~5$ ~i ~i N i 5 ~ , I I ~ ~
r~ i r--l N N ~ ~
-ri r--i O ~
'~ O
~ r ~ ~ ~ ~_ ~ ~
2 0 ~ ~ r--l O ~'~ I S-l I I I I I O O

Ln I i r~ a~ Ln N i I } } I } ~ UJ
r--i r1 ~ $
'O
r r-i r--i â~ C~ ~
O O ~ 0 00 O
~i ~r ~o ~ h I I I I I I O h ~ O ~ I~ r; ~i ~) ~3 i 1 7 7 , I
co ~ c) ~ ~ o i 7 ¦ I I i . rJi ~ ~1 r--l ~'f) ~i _ ~r-i _ ~ O ~î 0-- ~ ~
~ ~ N ~ Ln N ~ ~ ~O COLn r~ ~
ra $ ~ N ~ ~ N ~r CO Ln r~ ~n~r~
~ 3 r-J N ~ ~ ';1' Ln L
r--i I--i ~ _ _ _ _ _ _ _ _ _ _ r-_ o o o Ln o o o o o o tti ~n ' o o Ln L~ Ln o o Ln o Ln U~
~U~ ~) Ln 1` 1~ a~ o r--l (~ ~ ~ ~ ~) ¦~ l~ r-i r; r-!r i r-l rl ~;

~L~5~

Example ~9 Tests were conducted to determine the effects on water stability of various boron-containing compounds of formula (I) hereinbefore wherein R1 and R2 were unsubsti-tuted ethylene groups, M was hydrogen, and R contained between 8 and 20 carbon atoms and was either an alkyl group or an alkenyl group with only one double bond in the chain. The same tests were also conducted to determine the water stability of various boron-containing compounds of formula (II) hereinbefore wherein R4, R7, R8, Rg, R1o, R11, and M were hydrogen, R5 and ~6 were unsubstituted phenyl radicals (i.e., a benzene ring), and R3 varied as R
in formula tI~ discussed above.
The purpose of the experiment was to determine if, in the presence of water, said boron compounds would form an emulsion. A11 lubricating oils contain water (or come into contact with water) to some extent, and to the degree that the boron compound resists forming an emulsion in oil-water mixtures, to that same extent is it a more desirable additive for engine lubricating oils.
The tests were conducted as follows:
Into a test tube was placed sufficient water and lubricatiny oil containing the boron compound to be tested so that the water and oil each formed about 50 percent of the contents of the test tube. The contents were then shaken vigorously, after which the test tube was visually inspected to see if an emulsion had formed (indicative of water instability) or if two separate, clearly defined phases settlecl out (indicative of water stability).

~L~5~iO~

Upon visual inspection of the various samples, it was found that the boron compound of formula (II) consistently produced a clearly defined, two-phase liquid indicative of a boron additive stable to water in a lubricating environment. In contrast, the formula (I~
compound consistently formed an emulsion indicative of instability in the presence of water in a lubricating environment.
In yet other tests, it was found that the formula (II) compounds were less corrosive to lead and copper bearings in automotive engines and the like than the above-described formula (I) compounds.
From these tests, and the data shown in previous examples, the following was concluded: although the formula tI) compound is a highly useful lubricating oil additive, particularly in situa-tions wherein the water concentration of the oil can be minimized, the formula (II) compound possessed unexpectedly superior properties thereto with respect to water stability and corrosion inhibi.tionO

Example 90 I'he boron-containing heterocyclic compounds listed in Table 21 below were tested for oil solubility by adding 2 grams of each compound and separate samples of 98 grams of ~50 neutral oil to 250 ml Pyrex beakers equipped with teflon~coated, maynetic stirring bars which had lengths of 1-1/2 inches and diameter of 1/4 inch. The Pyrex beakers were placed on Model PC-351 Corning hot plates and the boron--containing heterocyclic compound-450 ~5~

neutral oil mixtures were heated at temperatures of 120 F. with stirring (400 RPM of stirring bars) for ten minutes.
The Pyrex beakers were removed from the hot plates and the boron-containing heterocyclic cornpound-450 neutral oil mixtures were examined for oil solubility of said compound in each sample. The results are summarized in the following Table 21:

760~ 25053-356 ~ , ~

-1 N ~ ~ U-) U~ I`

7~

The data in Table 21 show that boron-containing heterocyclic compounds are not soluble in 450 neutral oil at concen-trations of 2 weight percent when the ~ group attached to the nitrogen atom of said compounds contains 8 or less carbon atoms. In contrast, boron-containing heterocyclic compounds axe soluble in 450 neutral oil at concentrations of 2 weight percent when the R group contains 12 or more carbon atoms.
Based on these data, it is concluded that the oil solubility of the boron-containing heterocyclic compounds is directly related to the length of the carbon chain in the R group attached to the nitrogen a-tom of the amine moiety in said boron-containing heterocyclic compound, and that boron-containing heterocyclic compounds with 9 or more carbon atoms in the R group attached to the nitrogen atom of the amine moiety of said compounds are more soluble in oil than when said R group contains 8 or less carbon atoms.
Several other factors should also be considered when assessing the data in Table 21. One such is that the data are indicative of solubilities in a specific oil, i.e., a 450 neutral oil, and that for other oils, e.g., silicone synthetic oils, some of the boron compounds shown as insoluble may prove soluble. Thus, the data indicate the relative solubility of one boron compound versus another, not the absolute solubility of boron compounds in all oils. Another factor to be considered is the effect oE the length of the Rl and R2 groups. The data clearly indicate, when these groups contain only about 4 carbon atoms or less, that the solubility of the compound will be a function of the length of the R carbon chain. However, one can also increase the soluhility of the boron compounds by altering the Rl and R2 groups. For example~ compounds of formulae (II) and lIII) hereinbefore are soluble in 450 neutral oil, even when the R group side chain is relatively small. As an illustration, it is now known that a compound falling wi-thin foxmula (II), i.e., l-hydroxy--3,7-diphenyl-5-butyl-5-aza-1--bora-2,8-dioxacyclooc-tane, is known to be readily soluble in 450 neutral oil, despite the fact that the R group side chain is a relatively small butyl group.
Thus, the relative solubility of boron compounds herein are dependent on both the length of the R group side chain and the length and nature oE the Rl and R2 groups.

_xample 91 This Example compares the solubility and extreme pressure properties of boron compounds of the invention versus those disclosed in U.S. Patent 3,227,739.
The procedure described in Example 1 of U.S.
Patent 3,227,739 was followed to prepare M,N-diethanol 2-hydroxy C16-C18 amine with the following exception:
Since the EMC Corporation no longer commercially produces the C16-C18 epoxide used, 1,2 epoxyoctadecane was substituted for the FMC epoxide. The reaction produced N,N-diethanol, 2-hydroxy C18 amine.
The procedure described in Example 2 of U.S.
Patent 3,227,739 was followed to prepare the boric acid adduct of N,N~diethanol, 2--hydroxy C18 amine. The product thus produced (Compound A) was so]id at room temperature.

~5~
Test No. 1 The boric acia adduct of N,N-diethanol, 2-hydroxy C18 amine and the tallowaminodiethylate hydrogen borate (Compound B) produced in Example 2 hereinbefore were tested for oil solubility by adding the weight percentages indicated in Table 22 below to 450 neutral oil. The designated samples, including 450 neutral oil (100 grams ~otal), were added to 250 ml Pyrex beakers equipped with teflon-coated, magnetic stirring bars which had lengths of 2-1/2 inches and diameters of l/4 inch.
The Pyrex beakers were placed on Model PC-351 Corning hot plates and heated to the temperatures indicated in Table 22 with stirring (400 RPM of stlrring bars) for ten minutes.
The Pyrex beakers were removed from the hot plates, and the 450 neutral oil mixtures were examined for oil solubility of the respective compounds in each sample.
The results are su~marized in the following Table 22:

1~ 5 7 ~

o o ~ r r rY r-a~ ~ u~
~ ~ u~ O O 'O ,Y
~3 l -I r~ r I r~ r-l l~i cn o C~ U V~ C~ O
r~
r~ ~ u O O o o .~ o o o r~
~ ~4 ~ r ~ O ~ r ~
O ~ _ _ _ _ _ _ p~ CO
~ ~ ~ 14 h h h h h .~ Il ~ E~ ~ o o o o o o o~ ~
a~ ~ ~; ~9 w ~ r~ ~ ~ ~ ,_1 ~ ~P ~ ~

~ _ r~ 1~
~ ~ U~ O O Ln O o~ r4 O ~ o ,~ ~ o ,~ ~ .~i ~1- $
O ~ ,~

m m m '~
a ~ U ~ ~
u ~r~

,; ~ ~ ~r ~ u~ *

~5~

Several temperatures were used in an attempt to fully dlssolve Compound ~, i.e., the boric acid adduct of N,N-diethanol, 2-hydroxyamine, in 450 neutral oil. At temperatures of 130 F. (54.44 C.), 200 F. (93.33 C.) and 225 F. (107.22 C.), the compound was insoluble in 450 neutral oil. The compound was soluble in 450 neutral oil at 260 F.(126.~7 C.); however, upon cooling a cloudy appearance and sediment in the oil was noted. A concen-tration of 2 weight percent of Compound A produced a very viscous, semi-gel when mixed with 450 neutral oil and was unacceptable as an adclitive for the oil at this concentra-tion.
Compound B, i.e., tallowaminedie-thylate hydrogen borate, was fully soluble in all samples tested at the standard 130 F. (54.44 C.) mixing temperature for oil additives and did not precipitate from the oil upon standing and cooling.
Test No. 2 The boric acid adduct of N,N-diethanol, 2-hydroxy C18 amine and the tallowaminodiethylate hydrogen borate were also tested for oil solubility in the low phosphorus control SAE 30 motor oil (Example ~7) in accordance with the procedure described above. The results are summarized in the following Table 23:

7~0~i ~ ~ -5 ~
,~ ", .3 ~ ~ ~ a ~o o o o ~

~ ) O

r- ',~
~ _ ~_____ ~ ~ C~ o o o o o ~ ~
~1 h ~ ~ ~ ~r ~r ~ ~ ~) ~ o ~ ~;cO

~ ~ ~ __ ____ .~
~ O 1l o o o o O r~
tu ~) ~1 O O O O O o r-l r-l r j~j t~ ~I ~ ~ r-l ~1 ~ ~ ~
i~ ~ ~ ~
2 0 ~ _ O ~ U~ o o U~ o o o r; N O ~i ~i r~

~H

r~

~ ~ t4 '~ D
~ ~ ~ ~r u~ .1~ 1 7 ~

As shown in Table 23, Compound A was insoluble in the SAE 30 motor oil at all concentrations tested at temperatures of 130 F. (54.44 C.), 200 F. (93.33 C.) and 225 F. (107.22 C.). At a temperature of 260 F.
(126.67 C.), the compound did dissolve in the SAE 30 motor oil; however, upon standing, a sediment was noted in each sample.
By comparison, Compound B was soluble in the SAE
30 motor oil in all samples tested at a temperature of 130 F. (54.44 C.). The compound remained in solution and did not ~orm a precipitate or sediment in the oil upon standing.
Test_No. 3 The boric acid adduct of N/N-diethanol, 2-hydroxy C18 amine and tallowaminodiethylate hydrogen borate, both described above, were tested for extreme pressure proper-ties in accordance with the procedure disclosed in ASTM:D
3233-73 (Reapproved 1978) using a Falex lubricant tester.
The test, in accordance with the above ASTM designation, was performed by applying resistance ttorque) to a revolv-ing metal journal. A rachet mechanism movably attached to two V-blocks applied resistance by steadily increasing pressure on the journal. The metal journal and V~blocks, both construc-ted of steel, were submerged in the lubricant composition to be tested. The base oil in the experiments was the control SAE 30 motor oil (E,xample ~7). The SAE 30 motor oil was chosen as the base oil because the boric acid adduct of N,M-diethanol, 2-hydroxy C18 amine was slightly more soluble in this oil and did not produce a semi-gel at higher concentrations as compared to ~50 ~L~5~
neutral oil. However, this compound was not tested in the Fale~ luhricant tester at a concentration of 2 weight percent because at this concentration severe solubility problems were encountered in both the 450 neutral oil and the SAE 30 motor oil. The results are summarized in the following Table 24:

--10~--~L~5~

K ~ ~
~ ~1 O t~ OD O
o ~ ~ ~ n 3 o ~ $

o~
o ~o~
~3 ~ o ~ .
_ d, ~ ~ ~ _ _ .~
. O ~ Lrl ~ ~ N --1 00 ~ U~ ~0. ~ ~ C) E~ ~ ~ ~ ~ ~

20~ o~o~ ~ ~

0'~ ~ ~D O 'r~
~3~ o ~ ~ t~D O t ~ '~
~J t~) t.~l r-l t~ r-l ~ O ~ tl~
~ r-l t~ ~ tr) ~ t _ O O O UO~ ~ O ~ ~ r r~ 1 *

As shown in the foregoing Table 24, the compound prepared in accordance with the procedure of U.S. Patent 3,227,739 had inferior extreme pressure properties when compared with Compound B prepared according to the proce-dure of Example 2 hereinbefore. In contrast, the data in Table 24 show that tallowaminodiethylate hydrogen borate exhibits superior extreme pressure properties when added to SAE 30 motor oil as compared to the boric acid adduct of N,N-diethanol, 2-hydroxy C18 amine. And based on the data in Tables 22 and 23 above, compounds of the type disclosed in U.S Patent 3,227,73g experience oil solubility problems in 450 neutral oil and S~E 30 motor oil at concentrations of 0.5, 1.0, and 2.0 weight percent. In contrast, the tallowaminodiethylate hydrogen borate is completely soluble at such concentrations.

Exam~le 92 This example compares the solubility and extreme pressure properties of a compound disclosed in U.S. Patent 20 3,224,971 against the boron compounds produced according to Examples 1 and 2 hereinbefore.
The tris (borate ester) of bis (o-hydroxy-octyl-phenylmethyl) amine was prepared in accordance with the procedure in Example 3 (column 3, lines 39 to 69) of U.S.
Patent 3,224,971.
The borate ester was prepared by mixing 205 grams o~ 5-octylphenol, 23.4 grams of hexamethylene-tetramine and 500 ml of toluene in a single-necked one-liter round~bottomed flas}c. The flask was placed in a heating mantle and fitted with a Dean-Stark trap and -110~

~.~sc~jt7~

water-cooled condenser. The mixture was refluxed for 24 hours. Next, 20.6 grams of boric acid were added to the flask and the mixture was refluxed for an additional four hours during which water produced in the reaction was collected in the Dean-Stark trap.
Test No. 1 An experiment was performed to compare the boron compounds of Examples 1 and 2 hereinbefore with the borate ester described above in the Ryder~Gear Test disclosed in column 6, lines 1 to 48 and Table 6 of U.S. Patent 3,224,971. The base oil used in the -test was di-2-ethyl-hexyl sebacate.
A one-gram sample of the boron compound of Example 1 hereinbefore was admixed with 99 grams of di-2-ethyl-hexyl sebacate at 120 F. (48.89 C.) in a 250-ml Pyrex ~lass beaker. The boron compound did not dissolve in the base oil. The mixture ~ormed was cloudy and the boron compound settled to the bottom of the beaker upon standiny. The mixture was heated to 300 F. (148.89 C.); however, the boron compound did not dissolve in the di-2-ethyl-hexyl sebacate.
Next, a one-gram sample of the boron compound of Example 2 hereinbefore was admixed with 99 yrams of di-2-ethyl-hexyl sebacate at 120~ F. (48.89 C.) in a 200~ml Pyrex ylass beaker. This boron compound did not dissolve in the base oil. The base oil and boron compound mixture was heated to 300 F. (148.89 C.), but the boron compound still did not dissolve in the base oil.

~r~de ~c~/~J~

Additional experiments to determine the effective-ness of the two boron compounds as extreme pressure agents in the Ryder Gear Test were not conducted, because the compounds would not go into solution in the di-2-ethyl-hexyl sebacate base oil. However, experiments were conducted to compare the effectiveness in an SAE 10W 40 motor oil of these compounds and the tris borate esters of U.S. Patent 3,2249971 as extreme pressure agents in a Falex lubricant tester.
Test No. 2 The boron compounds of Examples 1 and 2 and the tris (borate ester) of bis (o-hydroxy-octylphenylmethyl) amine described above were tested in accordance with the procedure disclosed in ASTM D3233-73 (Reapproved 1978) using a Falex lubricant tester. The test was performed by applying resistance to a revolving metal journal. A
rachet mechanism movably attached to two V-blocks applied resistance by steadily increasing pressure on the journal.
The metal journal and V-blocks, both constructed of steel, were submerged in the lubricant composition to be tested.
The base oil in the experiments was an SAE 10W/40 motor oil marketed co~mercially by the Union Oil Company of California~ The results are summari~ed in the following Table 25:

5~

Table 25 Highest Jaw Load Before Failure, Composition Lbs.(Newtons) (1) SAE lOW/40 oil without any 1,400 (6,227) additive (2) SAE lOW/40 oil plus 1.0 wt.~ 1,700 (7,562) Example 1 compound (3) SAE lOW/40 oil plus 1.0 wt.% 2,250 (10,008) Example 2 compound (4) SAE lO~/40 oil plus 1.0 wt.% 900 (4,003) tris borate ester of bis (o-hydroxy-octylphenylmethyl~ amine (5) SAE lOW/40 oil plus 2.0 wt.% 900 (4,003) tris borate ester of bis (o-hydroxy-octylphenylmethyl) amine As shown in Table 25 above, the Example 1 and 2 compounds substantially increased the load carrying property (extreme pressure property) of SAE lOW/40 base oil in the Falex lubricant tester, while bis (o-hydroxy-octylphenylmethyl) amine had a detrimental effect upon the base oil, reducing the load carrying property of said oil by 500 pounds. The amount of bis (o-hydroxy-octylphenyl-methyl) amine added to the base oil was doubled with the same d~trimental effect noted.
Test No. 3 The boron compound of Example 1 hereinbefore and the tris (borate ester) of bis (o-hydroxy-octylphenylmethyl) amine described above were tested in accordance with the 1~5~6V~i procedure of Test No~ 2 with the Eollowing exception: 450 neutral oil marketed by the Union Oil Company of California was substituted for the SAE 10W/40 oil~ The results are summarized in the following Table 26:
Table 26 Highest Jaw Load Before Failure, ~E~ Lbs.(Newtons) (1) 450 neutral without additive 700 (3,114]

(2) 450 neutral oil plus 1.0 wt.% 1,100 (4,893) Example 1 compound (3) 450 neutral oil plus 1.0 wt.% 700 (3,114) tris borate ester of bis (o-hydroxy-oc-tylphenylmethyl) amine (4) 450 neutral oil plus 5.0 wt.% 700 (3,114) tris borate ester o~ bis (o-hydroxy-octylphenylmethyl) amine As shown in Table 26 above, the boron compound of Example 1 increased the load carrying property (extreme pressure) of 450 neutral base oil in the Falex lubricant tester. Bis (o-hydroxyoctylphenylme-thyl) amine did not affect the base oil either positively or negatively; the load-carrying property of the base oil was the same with or without the additive.

Example 93 The combination of a solution of an oil-soluble copper carboxylate such as cop~er naphthenate and a boron-containing heterocyclic compound both sulfurized and nonsulfurized gives better anti-wear protection in an oil than either component separately.
In the four~ball wear test (40 kg., 600 rpm, 167 F. (75 C.), 1 hour (ASTM D 4172-~2 modified to run at 600 rpm)), one loaded steel bal] rotates against three 7~ ;

stationary balls. The average wear scar diameter of the three stationary balls is a measure of wear. The reported wear scar diameters are the average scar diameters minus the Hertz scar diameter ~the average diameter in millimeters of an indentation caused by the deformation of the balls under static load, calculated from Dh = 8.73 x 10 2(p)1/3 where Dh is the Hertz diameter of the contact area, and P
is the static applied load).
The four-ball wear scar test was performed on an automotive oil (~50 neutral) containing the ingredients indicated in Table 27, with the results of the tests also being indicated therein. The borates of the invention all give better wear protection than copper naphthenate.
However, a combination of copper naphthenate solution and borates solution gives significantly better wear protection than either component alone. Therefore, there is a synergistic interaction between copper naphthenate and the borates of the invention.

~5~0~

s~

N c~ co 0 N ~D
t~ 1 ~ ~1 ~1 ~1 0 ~ OOOOOOO ~I

ro_ ~ ~ .
~ H ~ o O ~ ~

1 ~ I o I c~

2 0 ~

.~ ~ H ~1 ~ U

r~

Example 94 Tallowamine ~distilled~ from Armak Chemlcal Company (94.04 grams, 0.35 mole~, styrene oxide from Union Carbide (94.21 grams~ 0.70 moles) and -toluene (200 ml) were stirred at room temperature for 30 minutes in a round-bottomed flask equipped with a reflux condenser.
The mixture (solution) was heated to the reflux temperature of toluene for three hours producing an amine: styrene oxide adduct~ The adduct was cooled in the flask to room temperature (25 to 30C.) and boric acid (21.75 ~ram, 0.35 mole) was added. A Dean Stark-type water separation apparatus was inserted between the flask and condenserO
After 12.5 ml of water was collected in the Dean Stark sidearm, the reaction was presumed to be over. The flask and contents were then moved to a rotary evaporator to strip off the toluene leaving the product, l-hydroxy-3,7-diphenyl-5-tallow-5-aza-1-bora-2,8-dioxacyclooctane. This borate of the invention (75g~ and 100 ml of toluene are refluxed in a round-bottom flask~ 2.2g of sulfur is added to the refluxing mixture. The solution continued to reflux for 4 hours, then cooled to room temperature where 25g of 450 neutral oil is added and the toluene is elim-inated by rotary evaporation. The product is a brown, viscous sticky oil, i.e., a sulfurized form of l-hydroxy-3,7-diphenyl-5-tallow-5-aza-1-bora-2,8-dioxacyclooctane.

Obviously, many modifications and variations of this invention, as hereinbefore set for-th, may be made without departing from the spirit and scope thereof. For example, although the specification focused on the pre-ferred embodiment relating to oils for use in gasoline-powered automotive engines, the borates of the invention are useful in lubricating oils for diesel engines. In fact, it has been discovered that the borates of the inventlon, and especially the sulfurized version of 1-h~droxy-3,7-diphenyl-5-tallow-5-aza-1-bora-2,8-dioxa-cyclooctane, the most preferred borate of the present inven-tion, mar~edly reduce and/or prevent the formation of deposits in the upper ring zone of diesel engines, such as the caterpillar l-H2 Diesel Engine. Thus, it is intended that this embodiment of the invention and other such modifications and variations falling within the spirit and scope of the appended claims are embraced within the present invention.

Claims (85)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A boron-containing heterocyclic compound of the formula:

wherein:
y is an integer from 1 to 4;
M is selected from the group consisting of hydrogen, a metal from the periodic groups IB, IIB, IIIB, IVB, VB, VIB, VIIB, VIII, IIIA, IVA, VA, and organic radicals containing between 1 and 50 carbon atoms;
R is selected from the group consisting of hydrogen and organic radicals containing from 1 to 30 carbon atoms; and R1 and R2 are selected from the group consisting of organic radicals containing from 4 to 30 carbon atoms;
provided (1) that the compound does not contain sulfur (2) that, if M is hydrogen or an organic radical, then R1 and R2 each contains at least 4 carbon atoms and at least one of R1 and R2 is other than an unsubstituted or alkyl-substituted ortho-alkyl phenyl bridge with the oxygen connected to the phenyl carbon, and (3) R1 and R2 are free of amino groups.

2. The compound of claim 1 wherein R1 and R2 are the same or different alkylaryl radical.

3. The compound of claim 1 wherein M is a metal selected from the group consisting of the transition metals of atomic number between 21 and 30 and the Group IVA metals.

4. The compound of claim 1 wherein M is hydrogen.

5. The compound of claim 1 wherein M is neither hydrogen nor a metal.

6. The compound of claim 1 wherein at least one of R1 and R2 is a hydrocarbyloxy group of 4 to 30 carbon atoms.

7. The compound of claim 6 wherein the hydro-carbyloxy group is of formula:

wherein R17 is selected from the group consisting of alkyl, alkenyl, alkynyl, aryl, alkylaryl and arylalkyl radicals containing from 1 to 30 carbon atoms.

8. The compound of claim 7 wherein R is an alkyl or alkenyl group of l to 30 carbon atoms.

9. The compound of claim 1 wherein M is hydrogen and R contains at least 9 carbon atoms.

10. The compound of claim 1 wherein M is a hindered phenyl group substituted with an acetyl group, a methyl radical, or an -O-CH3 group.

11. The compound of claim 1 wherein M is a methyl group or a cyclohexyl radical.

12. The compound of claim 1, 3, or 4 wherein R is an alkylaryl or arylalkyl radical of at least 7 carbon atoms.

13. The compound of claim 1, 3, or 4 wherein both R1 and R2 are the same hydrocarbyloxy radical of 4 to 30 carbon atoms.

14. The compound of claim 4 wherein R is an alkenyl radical of 1 to 30 carbon atoms.

15. The compound of claim 1, 4, or 5 wherein neither R1 nor R2 contains a hydroxyl substituent.

16. The compound of claim 3, 4, or 5 wherein the linked atoms forming the bridge in both R1 and R2 between the oxygen and nitrogen atoms are all carbon atoms.

17. The compound of claim 3, 5, or 14 wherein R
contains at least 9 carbon atoms.

18. The compound of claim 3, 5, or 14 wherein R1 and R2 are both alkyl groups of 4 to 30 carbon atoms.

19. A lubricating composition comprising a major amount of a lubricating oil and a minor amount of the boron-containing heterocyclic compound of claim 1, 2, or 3.

20. A lubricating composition comprising a major amount of a lubricating oil and a minor amount of the boron-containing heterocyclic compound of claim 4, 5, or 6.

21. A lubricating composition comprising a major amount of a lubricating oil and a minor amount of the boron-containing heterocyclic compound of claim 7, 8, or 9.

22. A lubricating composition comprising a major amount of a lubricating oil and a minor amount of the boron-containing heterocyclic compound of claim 10, 11, or 14.

23. A boron-containing heterocyclic compound of the formula:

wherein:
y is an integer from 1 to 4;
M is selected from the group consisting of hydrogen, a metal from the periodic groups IB, IIB, IIIB, IVB, VB, VIB, VIIB, VIII, IIIA, IVA, VA, and organic radicals selected from the group consisting of alkyl, alkynyl, alkenyl, aryl, arylalkyl, and alkylaryl groups of between 1 and 30 carbon atoms;
R is selected from the group consisting of hydrogen and alkyl, alkynyl, alkenyl, aryl, arylalkyl, and alkylaryl groups of 1 to 30 carbon atoms; and R1 and R2 are selected from the group consist-ing of alkyl, alkynyl, alkenyl, aryl, arylalkyl, alkylaryl and hydrocarbyloxy groups of 4 to 30 carbon atoms, provided (1) that the compound does not contain sulfur, (23 that, if M is hydrogen or an organic radical, then R1 and R2 each contains at least 4 carbon atoms, (3) that R1 and R2 each bridge the respective oxygen atom and the nitrogen atom with carbon atoms, no one of which is a member of an aromatic ring, and (4) R1 and R2 are free of amino substitutions.

24. The compound of claim 23 wherein R1 and R2 are the same or different alkylaryl radical.

25. The compound of claim 23 wherein M is a metal selected from the group consisting of the transition metals of atomic number between 21 and 30 and the Group IVA metals.

26. The compound of claim 23 wherein M is hydrogen.

27. The compound of claim 23 wherein M is neither hydrogen nor a metal.

28. The compound of claim 26 wherein both R1 and R2 are hydrocarbyloxy groups of 4 to 30 carbon atoms.

29. The compound of claim 28 wherein the hydro-carbyloxy groups are both of formula:

wherein R17 is selected from the group consisting of alkyl, alkenyl, alkynyl, aryl, alkylaryl and arylalkyl radicals containing from 1 to 30 carbon atoms.

30. The compound of claim 23, 24, or 29 wherein M
is hydrogen and R contains at least 9 carbon atoms.

31. The compound of claim 23, 26, or 27 wherein R
is an alkyl or alkenyl group of 1 to 30 carbon atoms.

32. The compound of claim 23 wherein M is a hindered phenyl group substituted with an acetyl group or a methyl radical.

33. The compound of claim 23 wherein M is a methyl group or a cyclohexyl radical.

34. The compound of claim 25, 32, or 33 wherein R
is an alkyl or alkenyl group of 1 to 30 carbon atoms.

35. The compound of claim 23 wherein R is an alkyl-aryl or arylalkyl radical of at least 7 carbon atoms.

36. The compound of claim 29 wherein both R1 and R2 are the same hydrocarbyloxy radicals.

37. The compound of claim 25, 26, or 27 wherein R
is an alkenyl radical of 1 to 30 carbon atoms.

38. The compound of claim 14, 23, or 28 wherein the linked atoms forming the bridge in both R1 and R2 between the oxygen and nitrogen atoms are all carbon atoms.

39. The compound of claim 32 wherein R contains at least 9 carbon atoms.

40. The compound of claim 23 wherein M is a hindered phenyl group wherein the phenyl group is substituted at the 2 and 6 carbon atom of the phenyl ring with an alkyl radical having more than 3 carbon atoms.

41. The compound of claim 25, 26, or 27 wherein R1 and R2 are both alkyl groups of 1 to 30 carbon atoms.

42. The compound of claim 1, 32, or 40 wherein R1 and R2 are both alkyl groups of 1 to 30 carbon atoms.

43. The compound of claim 3, 4, or 5 where R1 and R2 are both phenyl radicals substituted with ethyl radicals, with the carbon atom of the ethyl radical which is bonded to the phenyl radical also being bonded to the oxygen atom.

44. A lubricating composition comprising a major amount of a lubricating oil and a minor amount of the boron-containing heterocyclic compound of claim 23 or 24,

45. A lubricating composition comprising a major amount of a lubricating oil and a minor amount of the boron-containing heterocyclic compound of claim 25, 26, or 27.

46. A lubricating composition comprising a major amount of a lubricating oil and a minor amount of the boron-containing heterocyclic compound of claim 28 or 29.

47. A lubricating composition comprising a major amount of a lubricating oil and a minor amount of the boron-containing heterocyclic compound of claim 32, 33, or 35.

48. A lubricating composition comprising a major amount of a lubricating oil and a minor amount of the boron-containing heterocyclic compound of claim 36, 39, or 40.

49. A boron-containing heterocyclic compound of the formula:

wherein:

y1 is an integer from 1 to 4;
M1 is selected from the group consisting of hydrogen, a metal from the periodic groups IB, IIB, IIIB, IVB, VB, VIB, VIIB, VIII, IIIA, IVA, VA, and organic radicals selected from the group consisting of alkyl, alkynyl, alkenyl, aryl, arylalkyl, and alkylaryl groups of between 1 and 50 carbon atoms; and R3, R4, R5, R6, R7, R8, R9, R10, and R11 are independently selected from the group consisting of hydrogen and alkyl, alkynyl, alkenyl, aryl, arylalkyl, and alkylaryl groups of 1 to 30 carbon atoms, provided (1) that the compound does not contain sulfur and (2) that at least two of R4, R5, R6, or R7 are aryl, arylalkyl, or alkylaryl radicals, and (3) that R6, R7, R8, and R9 are free of amino substitutions.

50. The compound of claim 49 wherein R5 and R6 are the same or different aryl, arylalkyl or alkylaryl radical.

51. The compound of claim 49 wherein R5 and R6 are both unsubstituted phenyl radicals, and R4, R7, R8, R9, R10, and R11 are all hydrogen.

52. The compound of claim 49 wherein M is a metal selected from the group consisting of the transition metals of atomic number between 21 and 30 and the Group IVA metals.

53. The compound of claim 51 wherein M is a metal selected from the group consisting of the transition metals of atomic number between 21 and 30 and the Group IVA metals.

54. The compound of claim 49 wherein M is hydrogen.

55. The compound of claim 51 wherein M is hydrogen.

56. The compound of claim 49 wherein M is neither hydrogen nor a metal.

57. The compound of claim 51 wherein M is neither hydrogen nor a metal.

58. The compound of claim 49 wherein R is an alkyl or alkenyl group of 1 to 30 carbon atoms.

59. The compound of claim 51 wherein R is an alkenyl radical of 1 to 30 carbon atoms.

60. The compound of claim 57 wherein R is an alkyl or alkenyl group of 1 to 30 carbon atoms.

61. The compound of claim 55 wherein R is an alkenyl radical of 1 to 30 carbon atoms.

62. The compound of claim 49 wherein M is a hindered phenyl group substituted with an acetyl group, a methyl radical, or an -O-CH3 group.

63. The compound of claim 51 wherein M is a hindered phenyl group substituted with an acetyl group, a methyl radical, or an -O-CH3 group.

64. The compound of claim 60 wherein M is a hindered phenyl group substituted with an acetyl group, a methyl radical, or an -O-CH3 group.

65. The compound of claim 64 wherein R contains at least 9 carbon atoms.

66. A lubricating composition comprising a major amount of a lubricating oil and a minor amount of the boron-containing heterocyclic compound of claim 49, 50, or 51.

67. A lubricating composition comprising a major amount of a lubricating oil and a minor amount of the boron-containing heterocyclic compound of claim 52, 53, or 54.

68. A lubricating composition comprising a major amount of a lubricating oil and a minor amount of the boron-containing heterocyclic compound of claim 55, 56, or 57.

69. A lubricating composition comprising a major amount of a lubricating oil and a minor amount of the boron-containing heterocyclic compound of claim 58, 59, or 60.

70. A lubricating composition comprising a major amount of a lubricating oil and a minor amount of the boron-containing heterocyclic compound of claim 61, 62, or 63.

71. A lubricating composition comprising a major amount of a lubricating oil and a minor amount of the boron-containing heterocyclic compound of claim 64 or 65.

72. A compound having the formula wherein R42, R43, R44, and R45 are independently selected from an alkyl, alkenyl, alkynyl, aryl, alkylaryl, or arylalkyl group of 1 to 10 carbon atoms, yg is an integer from 1 to 4, X2 and X3 are halogens, and Mg is selected from the group consisting of hydrogen, a metal from the periodic groups IB, IIB, IIIB, IVB, VB, VIB, VIIB, VIII, IIIA, IVA, VA, and organic radicals containing between 1 and 30 carbon atoms;
provided (1) that the compound does not contain sulfur (2) that, if Mg is hydrogen or an organic radical, then R44 and R45 each contains at least 4 carbon atoms and at least one of R44 and R45 is other than an unsub-stituted or alkyl-substituted ortho-alkyl phenyl bridge with the oxygen connected to the phenyl carbon, and (3) R44 and R45 are free of amino groups.

73. The compound of claim 72 wherein M is a metal selected from the group consisting of the transition metals of atomic number between 21 and 30 and the Group IVA metals.

74. The compound of claim 72 wherein M is hydrogen.

75. The compound of claim 72 wherein M is neither hydrogen nor a metal.

76. A lubricating composition comprising a major amount of a lubricating oil and a minor amount of the boron-containing heterocyclic compound of claim 73, 74 or 75.

77. A composition comprising a major amount of a lu-bricating oil and a minor amount of the compound of claim 3, 4, or 5 further comprising a minor proportion of at least one additive selected from the group consisting of:
(I) a compound of the formula:
wherein R46 and R47 are moieties selected from hydrogen or straight or branched chain alkyl, cyclic or alicyclic alkyl, aryl, alkylaryl or arylalkyl radicals having from 1 to about 30 carbon atoms, provided that R46 and R47 are not both hydrogen and w and z are numbers from 1 to about 8;
(II) terephthalic acid;
(III) a compound of the formula:

wherein M10 is a first row transition metal and t is an integer from 1 to 4; and (IV) a compound of the formula:

wherein R48 and R49 are the same or different alkyl radical having from 1 to 6 carbon atoms; and (V) a compound of the formula:

wherein R52 and R53 are hydrogen or the same or different alkyl radical having from 1 to about 30 carbon atoms.

78. A composition comprising a major amount of a lu-bricating oil and a minor amount of the compound of claim 24, 29, or 32 further comprising a minor proportion of at least one additive selected from the group consisting of:
(I) a compound of the formula:

wherein R46 and R47 are moieties selected from hydrogen or straight or branched chain alkyl, cyclic or alicyclic alkyl, aryl, alkylaryl or arylalkyl radicals having from 1 to about 30 carbon atoms, provided that R46 and R47 are not both hydrogen and w and z are numbers from 1 to about 8;
(II) terephthalic acid;
(III) a compound of the formula:

wherein M10 is a first row transition metal and t is an integer from 1 to 4; and (IV) a compound of the formula:

wherein R48 and R49 are the same or different alkyl radical having from 1 to 6 carbon atoms; and (V) a compound of the formula:

wherein R52 and R53 are hydrogen or the same or different alkyl radical having from 1 to about 30 carbon atoms.

79. A composition comprising a major amount of a lu-bricating oil and a minor amount of the compound of claim 39, 49, or 72 further comprising a minor proportion of at least one additive selected from the group consisting of:
(I) a compound of the formula:

wherein R46 and R47 are moieties selected from hydrogen or straight or branched chain alkyl, cyclic or alicyclic alkyl, aryl, alkylaryl or arylalkyl radicals having from 1 to about 30 carbon atoms, provided that R46 and R47 are not both hydrogen and w and z are numbers from 1 to about 8;
(II) terephthalic acid;
(III) a compound of the formula:

wherein M10 is a first row transition metal and t is an integer from 1 to 4; and (IV) a compound of the formula:

wherein R48 and R49 are the same or different alkyl radical having from 1 to 6 carbon atoms; and (V) a compound of the formula:

wherein R52 and R53 are hydrogen or the same or different alkyl radical having from 1 to about 30 carbon atoms.

80. A composition comprising a major amount of a lu-bricating oil and a minor amount of the compound of claim 23, 50, or 51 further comprising a minor proportion of at least two additives selected from the group consisting of:
(I) a compound of the formula:

wherein R46 and R47 are moieties selected from hydrogen or straight or branched chain alkyl, cyclic or alicyclic alkyl, aryl, alkylaryl or arylalkyl radicals having from 1 to about 30 carbon atoms, provided that R46 and R47 are not both hydrogen and w and z are numbers from 1 to about 8;
(II) terephthalic acid;
(III) a compound of the formula:

wherein M10 is a first row transition metal and t is an integer from 1 to 4; and (IV) a compound of the formula:

wherein R48 and R49 are the same or different alkyl radical having from 1 to 6 carbon atoms; and (V) a compound of the formula:

wherein R52 and R53 are hydrogen or the same or different alkyl radical having from 1 to about 30 carbon atoms.

81. A composition comprising a major amount of a lu-bricating oil and a minor amount of the compound of claim 14, 25, or 36 further comprising a minor proportion of at least three additives selected from the group consisting of: (I) a compound of the formula:

wherein R46 and R47 are moieties selected from hydrogen or straight or branched chain alkyl, cyclic or alicyclic alkyl, aryl, alkylaryl or arylalkyl radicals having from 1 to about 30 carbon atoms, provided that R46 and R47 are not both hydrogen and w and z are numbers from 1 to about 8;
(II) terephthalic acid;
(III) a compound of the formula:

wherein M10 is a first row transition metal and t is an integer from 1 to 4; and (IV) a compound of the formula:

wherein R48 and R49 are the same or different alkyl radical having from 1 to 6 carbon atoms; and (V) a compound of the formula:

wherein R52 and R53 are hydrogen or the same or different alkyl radical having from 1 to about 30 carbon atoms.

82. A composition comprising a major amount of a lu-bricating oil and a minor amount of the compound of claim 14, 55, or 61 further comprising a minor proportion of all of the following additives:
(I) a compound of the formula:

wherein R46 and R47 are moieties selected from hydrogen or straight or branched chain alkyl, cyclic or alicyclic alkyl, aryl, alkylaryl or arylalkyl radicals having from 2 to about 30 carbon atoms, provided that R46 and R47 are not both hydrogen and w and z are numbers from 1 to about 8;
(II) terephthalic acid;
(III) a compound of the formula:

wherein R48 and R49 are the same or different alkyl radical having from 1 to 6 carbon atoms.

83. A composition comprising a major amount of a lu-bricating oil and a minor amount of the compound of claim 25, 26, or 27 further comprising a minor proportion of all of the following additives:
(I) a compound of the formula:

wherein R46 and R47 are moieties selected from hydrogen or straight or branched chain alkyl, cyclic or alicyclic alkyl, aryl, alkylaryl or arylalkyl radicals having from 2 to about 30 carbon atoms, provided that R46 and R47 are not both hydrogen and w and z are numbers from 1 to about 8;
(II) terephthalic acid;
(III) a compound of the formula:

wherein R48 and R49 are the same or different alkyl radical having from 1 to 6 carbon atoms.

84. A composition comprising a major amount of a lu-bricating oil and a minor amount of the compound of claim 29, 40, or 52 further comprising a minor proportion of all of the following additives:
(I) a compound of the formula:

wherein R46 and R47 are moieties selected from hydrogen or straight or branched chain alkyl, cyclic or alicyclic alkyl, aryl, alkylaryl or arylalkyl radicals having from 2 to about 30 carbon atoms, provided that R46 and R47 are not both hydrogen and w and z are numbers from 1 to about 8;
(II) terephthalic acid;
(III) a compound of the formula:

wherein R48 and R49 are the same or different alkyl radical having from 1 to 6 carbon atoms.

85. A composition comprising a major amount of a lu-bricating oil and a minor amount of the compound of claim 57, 60, or 72 further comprising a minor proportion of all of the following additives:

(I) a compound of the formula:

wherein R46 and R47 are moieties selected from hydrogen or straight or branched chain alkyl, cyclic or alicyclic alkyl, aryl, alkylaryl or arylalkyl radicals having from 2 to about 30 carbon atoms, provided that R46 and R47 are not both hydrogen and w and z are numbers from 1 to about 8;
(II) terephthalic acid;
(III) a compound of the formula:

wherein R48 and R49 are the same or different alkyl radical having from 1 to 6 carbon atoms.