US3210278A

US3210278A - Metallic halide thiourea compounds

Info

Publication number: US3210278A
Application number: US247363A
Authority: US
Inventors: Ryer Jack; Paul M Kerschner; Walter C Bradbury
Original assignee: Cities Service Oil Co
Current assignee: Cities Service Oil Co
Priority date: 1962-12-26
Filing date: 1962-12-26
Publication date: 1965-10-05
Anticipated expiration: 1982-10-05

Description

United States Patent 3,210,278 METALLIC HALIDE THIOUREA COMPOUNDS Jack Ryer, East Brunswick, Paul M. Kerschner, Trenton, and Walter C. Bradbury, Newark, NJ., assignors to Cities Service Oil Company, a corporation of Delaware No Drawing. Filed Dec. 26, 1962, Ser. No. 247,363 18 Claims. ((31. 252-46.4)

This application is a continuation-in-part of application Serial No. 502, filed January 5, 1960, now abandoned.

This invention relates to new organo metallic compounds and more particularly to divalent metal halide organo metal complexes of thiourea and to a method for preparing the same.

There has been in recent years a growing interest in the combination of organic radicals and metals to provide new and unique structures having a variety of characteristics and properties which serve a multitude of purposes. New organo-metallic structures have been found particularly useful as catalysts, solvents, chemical intermediates, additives and in many other applications.

The present invention is directed to a new series of compounds of this type; more particularly metallic halidethiourea complexes having the general structure wherein X is a halogen selected from the group consisting of chlorine bromine and iodine, M is a divalent metal selected from the gnoup consisting of zinc, cadmium and manganese, R and R represent a substituent selected from the group consisting of hydrogen, alkyl having from .3 to 20 carbon atoms, alicyclic having from 6 to 20 carbon atoms, amine substituted acyclic having from 2 to 11 carbon atoms, aralkyl having from 7 to 20 carbon atoms, and aryl, and R" and R represent a substituent selected from the group consisting of alkyl having from 3 to 20 carbon atoms, alicyclic having from 6 to 20 carbon atoms, amine substituted acyclic having from 2 to 11 carbon atoms, a-ralkyl having from 7 to 20 carbon atoms, and aryl.

The divalent metal halide-thiourea compounds of the present invention are prepared by first synthesizing an intermediate N, N or N, N, N, N, substituted thiourea which is thereafter reacted with a divalent metal halide to produce a complex having the structure shown in the general formula. Quite unexpectedly these new compounds have been found to be most effective as extreme pressure additives when utilized in small amounts in various lubricating compositions which include synthetic, as well as mineral oil base lubricants.

In preparing lubricant compositions with the extreme pressure agents of the present invention it has been found that an amount of additive of from 0.05% to about 15.0% by weight makes a most satisfactory lubricant composition. Preferably, the agent or extreme pressure additive will be used in an amount of from 0.1 to about 10% by weight of the base lubricant material. In preparing these new lubricant compositions, it has been found that a wide variety of both mineral oil and synthetic base stocks, including mixtures of the same, can be used. Suitable mineral oil base materials include 100 and 200 neutral oils, light and heavy intermediate mineral oils, bright stock and as well as combinations of the foregoing. If a synthetic base material is used diesters, polyesters, silicones, silicates, fluorocarbons, phosphates, polyglycols and polyphenyl ethers and mixtures of the same may be used.

3,210,278 Patented Oct. 5, 1965 In carrying out the preparation of these extreme pressure compounds according to the method of this invention two mols of an amine are reacted with one mol of carbon disulfide in the presence of a suitable hydrocarbon solvent such as benzene, toluene, xylene, propylbenzene or the like, under reflux conditions determined by the particular solvent utilized. As the reaction between the amine and carbon disulfide progresses hydrogen sulfide is evolved. The reaction is completed when hydrogen sulfide ceases to be evolved. The substituted thiourea product obtained is dissolved in an alcohol solvent such as ethanol, propanol, isopropanol, butanol, isobutanol, or the like, and heated to boiling. To this solution a hot alcohol solution of a selected metal halide is added. A substantially instantaneous reaction occurs producing a divalent metal halide substituted thiourea complex. The latter reaction is carried out in a molar ratio of approximately one mol of substituted thiourea to one-half mol of the metallic halide. If this reaction is not immediate on mixing, a gentle reflux may be applied at a temperature dependent on the solvent utilized. In selecting the latter, it is essential that the solution of the substituted thiourea and the solution of the metallic halide be mutually miscible. If reflux is carried out, either in the initial reaction leading to the preparation of the substituted thiourea or in the reaction of the latter with the metallic halide, periods of up to 12 hours or more may be necessary to bring about a completed reaction.

In preparing the substituted thiourea it has been found that aliphatic amines having from 3 to 20 carbon atoms, either straight chain or branched chain, as well as cyclic, aromatic or substituted aromatic amines, or mixtures thereof may be used. The amine may be a primary or secondary amine and may include unsaturation in a chain or ring structure. Suitable amines for preparing the intermediate substituted thiourea include the following: propylamine, butylamine, pentylamine, hexylamine, cyclo hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, benzylamine, heptadecylamine, octadecylamine, nonadecylamine, eisosanylamine, diethylamine, N-ethylpropylamine, dipropylamine, N-propylbutylamine, dibutylamine, N- butylpentylamine, dipentylamine, N-pentylhexylamine, dihexylamine, N-hexylheptylamine, diheptylamine, N- heptyloctylamine, dioctylamine, N-octylnonylamine, dinonylamine, N-nonyldecylamine, didecylamine, N-methylpentylamine, N-methylhexylamine, N-ethylpentylamine, N-ethylhexylamine, N-propylpentylamine, N-propylhexylamine, N-butylhexylamine, N-methylheptylamine, N ethylheptylamine, N-propylheptylamine, N-butylheptylamine, N-methyloctylamine, N-ethyloctylamine, N-propyloctylamine, N-butyloctylamine, N-pentyloctylamine, N-methylnonylamine, N-ethylnonylamine, N-propylnonylamine, N-butylnonylamine, N-pentylnonylamine, N-hexylnonylamine, N-methyldecylamine, N-ethyldecylamine, N-propyldecylamine, N-butyldecylamine, N-pentyldecylamine, N-hexyldecylamine, N-heptyldecylamine, phenylbutylamine, and N-octydecylamine. Lower molecular weight acyclic polyamines such as di-N-butylaminopropylamine, ethylenediamine, diethylenetriamine, triethylenetriamine, and triethylenetetramine may be used.

In the foregoing general formula the amine residues are represented by R, R, R and R. These substituents may of course be similar or dissimilar depending on the amines selected in preparing the aminothiourea. If two mols of a primary amine are used, R and R will represent hydrogen with R and R representing the residues of the amine chain. If secondary amines of a mixture of secondary and primary amines are used, R, R, R and R' will represent the residues of the respective amines used.

The divalent metal halide selected for reaction with the substituted thiourea will be a halide of a metal selected from the group consisting of zinc, cadmium and manganese. It is preferred that the halogen be either chlorine, bromine or iodine. As previously indicated, a hot alcoholic solution of the divalent metal halide is prepared and reacted with an alcoholic solution or equivalent solvent solution of the substituted thiourea. After this reaction has been completed excess solvent is removed from the reaction zone by distillation. Trace residues of unreacted thiourea may be removed from the reaction zone by distillation under vacuum.

The examples which follow will provide a more complete understanding of the new compounds and their manner of preparation, as Well as the lubricant compositions in which these compounds are used.

EXAMPLE 1 To a one liter flask equipped with a stirrer, reflux condenser and dropping funnel, 398 gms. (2 mols) of Primene 81R (a Rohm & Haas mixed primary amine product) the residue formula of which is and 100 ml. toluene were added. 76 gms. (1 mol) of carbon disulfide was added dropwise to the flask. The temperature was maintained in the range of from 20 to 30 C. during addition of the carbon disulfide. After the carbon disulfide was added, the mixture was refluxed at a temperature of 100 i C. and maintained at this temperature for 12 hours. After this time no further evolution of H 8 was noted. The reaction mixture was cooled to room temperature and the toluene solvent removed from the reaction flask by distillation with trace removal of toluene and unreacted amine being accomplished under vacuum. A 99.3% yield of the desired compound S=C[NHC(CH (C H was obtained. One mol of this product (440 gms.) was dissolved in 50 ml. of isopropyl alcohol and heated to boiling. 68 gms. (0.5 mol) of zinc chloride, dissolved in a minimum amount of hot isopropyl alcohol, was slowly added with stirring to the boiling alcoholic disubstituted thiourea solution. The mixture was allowed to cool to room temperature and excess isopropyl alcohol was stripped by distillation from the reaction product complex. An 88% yield of the complex was obtained. The compound is a liquid, reddish brown in color and has a molecular Weight of 1016. An analysis of this compound showed 5.9% by weight of zinc and 5.3% by Weight of sulfur. The calculated weight percentage for zinc and sulfur are 6.4% and 6.3% respectively. The eifectiveness of this compound as an extreme pressure additive is demonstrated in the table which follows wherein the compound is identified as D.

EXAMPLE 2 Following the procedure set forth in Example 1 dichlorobis-N,N'-dicyclohexylthioureazinc was prepared by first reacting 198 gm. (2.0 mol) cyclohexylamine with 76 gm. (1.0 mol) carbon disulfide in the presence of ethanol and a small amount of potassium hydroxide. After evolution of hydrogen sulfide ceased excess ethanol was removed from the reaction zone by distillation. An isopropyl alcohol solution of 68 gms. (0.5 mol) zinc chloride was added to a boiling isopropyl alcohol solution N, N dicyclohexylthiourea. Excess alcohol was re moved from the reaction mixture leaving a light colored liquid product of dichlorobis-N,N'-dicyclohexylthiourea zinc (Cl Zn[S=C(NHC H EXAMPLE 3 Following the procedure set forth in Example 1 dichlorobis-N,N'-di-n-butylthioureazinc was prepared by reacting two mols of n-butylamine with one mol of carbon disulfide to yield an N,N-di-n-butylthiourea intermediate which was thereafter reacted with one-half mol of an alcoholic solution of zinc chloride to yield dichlorobis- N,N n butylthioureazinc (Cl Zn(S C(NI-IC H This compound has a molecular weight of 512 and contained 12.9% zinc. The efiectiveness of this compound as an extreme pressure additive is demonstrated in the table which follows, wherein the compound is identified as A.

EXAMPLE 4 Two mols of n-hexylamine were reacted according to the method of Example 1 with one mol of carbon disulfide under reflux conditions in the presence of approximately ml. of toluene until the evolution of hydrogen sulfide ceased. The N,N' di nhexylthiourea obtained when reacted with a hot isopropyl alcohol solution of zinc chloride yielded dichlorobis N,N-di-n-hexylthioureazinc (Cl Zn[S=C(NHC H having a molecular weight of 616. This compound analyzed as followspercent zinc by weight 9.7, percent sulfur by weight 9.2.

EXAMPLE 5 Two mols of di-n-butylaminopropylamine a Q) 2 2) a z) were reacted according to the method of Example 1 with one mol of carbon disulfide under reflux conditions in the presence of toluene until the evolution of hydrogen sulfide ceased. One mol of the N,N' di(di n butylaminopropyl) thiourea obtained was reacted with a hot isopropyl alcohol solution of one-half mol of zinc chloride to yield dichlorobis-N,N'-di-(di-n-butylarninopropyl) thioureazinc (ClgZXl[S C(NHC3H N(C4H9)2)2]2). compound has a molecular weight of 976 and analyzed as follows:

Percent S: Found, 6.3; calculated, 6.6.

EXAMPLE 6 EXAMPLE 7 Two mols of dodecylamine were reacted according to the foregoing examples with one mol of carbon disulfide under reflux conditions in the presence of toluene until the evolution of hydrogen sulfide ceased. The N,N'-didodecylthiourea obtained was then reacted with a hot isopropyl alcohol solution of zinc chloride to yield dichlorobis-N,N-di-dodecylthioureazinc having a molecular weight of 960, 6.9% by weight of zinc and 6.2% by weight of sulfur. The calculated values for this compound of zinc and sulfur are 6.8 and 6.7 respectively. The compound is identified as B in the table which follows.

EXAMPLE 8 Two mols of Armeen-C (a mixed aliphatic amine prodnot of the Armour Co. having the formula were reacted according to the method of Example 1 with one mol of carbon disulfide .under reflux conditions until the evolution of hydrogen sulfide ceased. The mixed dialkyl substituted thiourea obtained was reacted with a hot isopropyl alcohol solution of zinc chloride in a molar 'ratio of 2:1 to yield a zinc chloride complex of the mixed dialkyl substituted thiourea.

EXAMPLE 9 Two mols of phenylamine were reacted according to the method described in the foregoing examples with one mol of carbon disulfide under reflux conditions in the presence of xylene until no further hydrogen sulfide evolution was noted. After removal of solvent an alcohol solution of N,N'-diphenylthiourea was reacted with one-half mol of zinc chloride to yield dichlorobis-N,N'-diphenylthioureazinc (C1 Zn [S=C (NHC H EXAMPLE 10 Two mols of oleylamine were reacted according to the method of Example 1 with one mol of carbon disulfide under reflux conditions in the presence of toluene until the evolution of hydrogen sulfide was completed. The N,N-dioleylthiourea obtained was thereafter reacted in the manner previously described with zinc chloride to yield dichlorobis-N,N'-dioleythioureazinc z 1a 35)2)2 This compound is identified as C in the table following.

EXAMPLE 11 Two mols of Primene JM-T (a Rohm & Haas mixed amine commercially available product having the following carbon chain structure(C(CH (C H was reacted according to the method previously described with one mol of carbon disulfide to yield a disubstituted thiourea. This intermediate was then reacted with an alcohol solution of zinc chloride in a molar ratio of 2:1 to yield a dichlorothioureazinc complex identified as compound E in the table.

EXAMPLE 12 Two mols of Primene 81R were reacted with one mol of carbon disulfide to yield an intermediate disubstituted thiourea which was thereafter reacted with an alcoholic solution of cadmium chloride in the manner previously described to yield the dichlorocadmium complex of the disubstituted thiourea. The product obtained 4.6% cadmium by weight and 3.8% sulfur.

EXAMPLE 13 Two mols of Primene 81R were reacted with one mol of carbon disulfide to yield an N,N' disubstituted thiourea which was thereafter reacted in a molar ratio of 2:1 with manganese chloride according to the method described above to yield the dichloromanganese complex of the disubstituted thiourea. This product is identified as compound F in the table.

EXAMPLE 14 To a one liter flask equipped with a stirrer, reflux condenser and dropping funnel, 2 mols of Primene 81R and 100 ml. of toluene are added. One mol of carbon disulfide is added dropwise to the flask. The temperature is maintained within the range of to C. during the addition of the carbon disulfide. After the addition, the mixture is refluxed at a temperature of 100 i10 C. and maintained at this temperature until reaction mixture is cooled to room temperature and the toluene solvent is removed by distillation in vacuo with trace removal of toluene and unreacted amine. Two mols of this product is reacted with one mol of zinc bromide dissolved in a minimum amount of hot isopropyl alcohol. The mixture is cooled to room temperature and excess alcohol stripped from the reaction product. The dibromozinc complex of the disubstituted thiourea is thereby obtained.

EXAMPLE 15 To a one liter flask equipped with a stirrer, reflux condenser and dropping funnel, 186 gms. (2 mols) of aniline and ml. of toluene are added. 76 gms. (1 mol) of carbon disulfide are added dropwise to the flask. The temperature is maintained within the range of 20 to 30 C. during the addition of the carbon disulfide. After the addition, the mixture is refluxed at a temperature of 100 :10 C. and maintained at this temperature until no further evolution of H 8 is noted. The reaction mixture is cooled to room temperature and the toluene solvent is removed by distillation in vacuo with trace removal of toluene and unreacted amine. The compound is thereby obtained. One mol of this product is reacted with 0.5 mol (63 gms.) of manganese chloride dissolved in a minimum amount of hot isopropyl alcohol. The mixture is cooled to room temperature and excess alcohol stripped from the reaction product complex. Dichlorobis-N,N-diphenylthioureamanganese is thereby obtained. An analysis of this compound shows 10.5 percent by weight of manganese and 12.2 percent by weight of sulfur.

EXAMPLE 16 To a one liter flask equipped with a stirrer, reflux condenser and dropping funnel, two mols (214 gms.) of benzylamine and 100 ml. of toluene are added. One mol (76 gms.) of carbon disulfide is added dropwise to the flask. During the addition, the temperature is maintained within the range of 20 to 30 C. The mixture is refluxed at 100 i10 C. until no further evolution of H 8 is noted. The reaction mixture is allowed to cool to room temperature and the toluene solvent removed by distillation in vacuo with trace removal of toluene and unreacted amine. The compound is obtained as a reaction product. One mol of this compound is reacted With 0.5 mol (136 gms.) of cadmium bromide dissolved in hot isopropyl alcohol. The mixture is cooled to room temperature and excess alcohol stripped therefrom. Dibromobis-N,N-dibenzylthioureacadmium (Br Cd[S=C(NHCH C H 1 is obtained as a reaction product.

EXAMPLE 17 Two moles (196 gms.) of cyclohexylamine in toluene are reacted with one mol (76 gms.) of carbon disulfide under reflux conditions. At the cessation of H 8 evolution, the mixture is allowed to cool to room temperature. One mol of the reaction product is reacted with 0.5 mols (183 gms.) of cadmium iodide dissolved in a minimum amount of hot isopropyl alco-' hol. The mixture is cooled to room temperature and excess alcohol stripped from the reaction product complex. Diiodobis-N,Ndicyclohexylthioureacadmium 2 s 11)2]2) is obtained as a reaction product.

EXAMPLE 18 To a one liter flask equipped with a stirrer, reflux condenser and dropping funnel, 2 mols (262 gms.) of N', N"dimethyl diethylenetriamine and 100 ml. of toluene are added. One mol (76 gms.) of carbon disulfide is added dropwise at a temperature of 20 to 30 C. The mixture is refluxed until no further H 8 evolution is noted. The reaction mixture is cooled to room temperature and the toluene subsequently removed. The reaction product obtained has the formula [hc NH c H NHc HrN(C s)21z One mole of this compound is reacted with 0.5 mol (68 have been demonstrated to have increased load carrying properties.

Typical examples of these oils including the specific amounts of additive to provide the improved load carry- 5 ing characteristics will be apparent from the table which 0f Zlnc chloflde dissolved in hot P PY alcofollows wherein data is provided on the test results car- 1101. Th6 IniXtllTe is cooled room temperature and ried out in a standard Shell 4 ball test procedure. excess alcohol pp therefrom The complex The standard Shell 4 ball test is based on the use of chlol'obis s y y l an apparatus that includes 3 rigidly held /2" metal balls realiflc) 2 2 4 2 4 3)a)2]2 is 10 (type 52-100 steel balls) submerged in the lubricant to Obtain d as a rea tion p odu t. be tested in a metal cup. A 4th ball of the same size EXAMPLE 9 and material is pressed into contact with the 3 fixed balls by an adjustable loading arm and allowed to rub over Accordlng to the Procedures Ex'ample W mol a fixed period of time. The contact points on the 3 (129 gms-) of N'propylamlflamme 1S reacted g 15 stationary balls grow to circular scars as Wear progresses. mol (38 of carbon dlsulfide Produce The average diameter of these scars in mms after the propylamylthiourea. 0.5 mol 0f th P d 15 reacted fixed period of operation at a particular speed and load f 025 .gmsJ of P- bromlfie to Produce is taken as a measure of wear. The temperature at which dlbmmobls'NrN 'dlpropylamylthloureacadmlum the test is carried out may be varied from room tempera- (B Cd[S::C(N(C I-I )(I l-1 0 1 ture to as high as 170 C.

Table I.-Extreme pressure properties of lubricating oil compositions determined as seizure and weld in the shell four ball machine (kilograms of load) Compound A B C D E F Wt. percent additive in Seizure Weld Seizure Weld Seizure Weld Seizure Weld Seizure Weld Seizure Weld Plexol 201:

0.0 110 55 110 55 110 55 110 55 110 0.3 75 160 05 140 1.0- 145 60 115 50 130 5.0- 170 120 190 110 170 10.0- 110 225 110 170 Neutral:

0.0 45 45 110 45 110 45 110 45 110 45 110 1.0 100 175 110 70 140 70 5.0- l. 100 190 135 205 120 170 10.0. 100 220 175 345 110 210 Heavy Intermediate eutral: 0.0 65 125 65 125 65 125 65 125 65 125 65 125 1.0 110 120 190 80 150 7 140 5.0- 90 310 110 210 130 10.0- 190 370 130 230 1 Additive insoluble in base oil.

EXAMPLE 20 Dichlorobis-N,N-dibutylamylthioureazinc is prepared by reacting one mol of N-butylamylamine with 0.5 mol of carbon disulfide under reflux conditions in the presence of toluene. The reaction product is then reacted with zinc chloride. The final reaction product is Obtained by the procedures described hereinbefore.

EXAMPLE 21 Dichlorobis-N,N-dibutylhexylthioureazinc 2 4 9) ti 13)2:l2)

is prepared by reacting one mol (157 gms.) of N-butylhexylamine with 0.5 mol (38 gms.) of carbon disulfide under reflux conditions in the presence of toluene. 0.5 mol of the disubstituted thiourea product is then reacted with 0.25 mol of zinc chloride. The final reaction product is obtained by the procedures previously described.

As has been previously indicated the organo-metallie compounds of the present invention unexpectedly provide extreme pressure characteristics for lubricating compositions when added to the same. It has been pointed out that the compounds of the present invention may be added to various mineral and synthetic base stocks in amounts of from .05 to 15 weight percent and preferably from 0.10 to 10.0% by weight. Lubricant compositions prepared with varying amounts of these compounds In the foregoing table Plexol 201 is the synthetic lubricant (Z-Ethylhexyl Sebacate manufactured by Rohm & Haas, Philadelphia, Penn. The 100 Neutral is a base mineral oil having an API gravity of 32 (min.) specific gravity (max) 0.8654; flash COC F. (min.) 380; fire COC F. (min.) 430; viscositySUS at 100 F. 100410; at 210 F. 40; VI range (min.) 95 and pour point F. (max) 0. The Heavy Intermediate base stock used has the following specification-API gravity 28 (min.), specific gravity (max) 0.8871; flash COC F. (min.) 510, fire COC F. (min.) 570; viscosity-SUS at 100 F. 632-7l2; at 210 F. 70-74; VI range (min.) 95 and pour point F. (max) 5.

Referring to Table I, it will be noted that the addition of comparatively small amounts of the new compounds of the present invention substantially improved in every instance the load carrying and extreme pressure characteristics of the lubricating composition to which added. For example, in the composition of 100 Neutral lubricating oil 1% of Compound C increased the seizure load more than 100% and the weld load approximately 50%. In a like manner the addition of Compound D to 100 Neutral oil in the amount of 1% increased the seizure load over 100% and the Weld load approximately 35%. When increased to 5% by weight Compound D increased the load carrying property of 100 Neutral from 45 to 135 and the weld load from 110 to 205. In substantially all other cases similar increases are to be noted.

In the examples which follow, representative samples of lubricant compositions prepared with varying base materials including mixed base stocks and representative extreme pressure agents are set forth.

Dibromo bis N,N' dipropylamylthiourea cadmium product Example 19) In the table which follows, data is set forth demonstrat ing the effectiveness of the additives of the present invention in lubricant compositions prepared from mixtures of the additive and base stock materials.

Table lI.Tz'mken lubricant test [Conditions 110 F., 800 r.p.m.]

for the lubricant composition and the final characteristics desired in the composition. Typical antiaoxidants which may be used for this purpose are phenothiazine, phenylcz-naphthylamine, 2,6-ditertiarybutyl-p-cresol and diphenyl-p-phenylenediamine. Suitable viscosity improvers in clude the following: polyacrylates, polyisobutylenes and polyvinyls. If a pour point depressant is desired, small amounts of one or more of the following materials may be added: condensation product of naphthalene and parafiin wax, polyacrylates and acrylate-vinyl copolymers.

While we have described our invention with some degree of particularity with respect to the structures of the compounds and the method by which the compounds may be prepared, it is to be understood that we intend to limit the same only in the manner provided by the claims appended hereto.

We claim:

1. A lubricating composition having extreme pressure properties comprising a major amount of an oil base material and from about 0.05 to about 15.0% by weight of a compound having the formula Percent OK load Scar Condition Base stock Additive additive (1b.) diam. of test block 200 Neutral, 150

Bright Stock None 10 0.9 Pass. 37.5% 200 Neutral, 57

150 Bright Stock A 5 40 1. 62 Do.

Note.Additive A is diehlorobis-N,N'-dialkylthiourea zinc wherein the alkyl group is the miXtureC(CH3)2 1iHm-z3 (product Example 1).

Base stock Additive Percent No. of Scar Condition of additive teeth req. width in 60% Hvy. t. Neut., 40%

Lt. Int. Neut None 0 Sheared pin 59.75% Hvy. Int. Neut., at 750 p. s.i. 39.75% Lt. Int. Neut A 0.5 0 0.3 No corrosion. 57.5% Hvy. Int. Neut.,

37.5% Lt. Int. Neut A 5 0 0.3 Do.

Table IV.Mac Coull corrosion test @350 F. 60 aralkyl having from 7 to 20 carbon atoms and aryl and R" and R each represents a substituent selected from Base Stock Additive Pemqnt Bearing Acid the group consistmg of alkyl having from 3 to 20 carbon addltlv 1 a atoms, alicyclic having from 6 to 20 carbon atoms, amine substituted acyclic having from 2 to 11 carbon atoms, 51 7; g g t, None 0 200 5 aralkyl having from 7 to 20 carbon atoms and aryl. ,i I ];I53;j%" 2. A lubricating composition as claimed in claim 1 vy. Int. Neut A 0.6 wherein X is chlorine, M is manganese, R and R are hy- In preparing the compositions of the present invention, it may be desirable to improve certain properties and characteristics of the composition by utilizing various known additives such as anti-oxidants, color stabilizers, viscosity improvers, pour point depressants, anti-foam agents and detergents. These materials will be added in varying amounts depending on the particular use intended 1 1 wherein X is chlorine, M is zinc, R and R are hydrogen and R" and R' are C H NHC H N(CH 6. A lubricating composition as claimed in claim 1 wherein X is iodine, M is cadmium, R and R are hydrogen and R and R are C H 7. A mineral oil lubricating composition having extreme pressure properties comprising a major amount of a mineral oil base material and from about 0.5% to about 15.0% by weight of a compound having the formula R or i l-R" M-S=C C R wherein M is a metal selected from the group consisting of zinc, cadmium and manganese, R and R each represents a substituent selected from the group consisting of hydrogen, alkyl having from 3 to 20 carbon atoms, alicyclic having from 6 to 20 carbon atoms, amine-substituted acyclic having from 2 to 11 carbon atoms, aralkyl having from 7 to 20 carbon atoms and aryl and R and R' each represents a substituent selected from the group consisting of alkyl having from 3 to 20 carbon atoms, alicyclic having from 6 to 20 carbon atoms, amine-substituted acyclic having from 2 to 11 carbon atoms, aralkyl having from 7 to 20 carbon atoms and aryl.

8. A mineral oil lubricating composition as claimed in claim 7 wherein M is zinc, R and R are hydrogen and R and R are G l-I 9. A mineral oil lubricating composition as claimed in claim 7 wherein M is zinc, R and R are hydrogen and R and R are C H 10. A mineral oil lubricating composition as claimed in claim 7 wherein M is manganese, R and R are hydrogen and R" and R are C H 11. A mineral oil lubricating composition as claimed in claim 7 wherein M is zinc, R and R are Cid-I and R and R are C l-I 12. A mineral oil lubricating composition as claimed in claim 7 wherein M is zinc, R and R are hydrogen and R" and R are C I-I 13. A lubricating composition having extreme pressure properties comprising a major amount of synthetic oil base stock and from about 0.05% to about 15.0% by weight of a compound having the formula wherein M is a metal selected from the group consisting of zinc, cadmium and manganese, R and R each represents a substituent selected from the group consisting of hydrogen, alkyl having from 3 to 20 carbon atoms, alicyclic having from 6 to 20 carbon atoms, amine-substituted acyclic having from 2 to 11 carbon atoms, aralkyl having from 7 to 20 carbon atoms and aryl and R and R each represents a substituent selected from the group consisting of alkyl having from 3 to 20 carbon atoms, alicyclic having from 6 to 20 carbon atoms, amine-substituted acyclic having from 2 to 11 carbon atoms, aralkyl having from 7 to 20 carbon atoms and aryl.

14. A lubricating composition comprising an oil base stock composition as claimed in claim 13 wherein M is zinc, R and R are hydrogen and R and R are C H 15. A lubricating composition comprising an oil base stock composition as claimed in claim 14 wherein M is manganese, R and R are hydrogen and R and R' are C l-I 16. A lubricating composition comprising an oil base stock composition as claimed in claim 15 wherein M is zinc, R and R are C H and R and R are C H 17. A lubricating composition having extreme pressure properties comprising a major amount of an oil base material and from about 0.05% to about 15.0% by weight of an additive containing mixed alkyl compounds of the formula:

wherein each of R" and R is alkyl having from about 9 to about 11 carbon atoms, R and R' for each alkyl compound difiering from that of the other alkylcompounds in said additive.

References Cited by the Examiner UNITED STATES PATENTS 12/33 Estabrooke 260429 1,938,585 2,704,745 3/55 Kopp et al 252-475- 2,849,420 8/58 Stevens et a1 260429 OTHER REFERENCES Engle et al.: B35712IVc/23c, June 21, 1956 (German patent application).

DANIELE. WY MAN, Primary Examiner.

Claims

1. A LUBRICATING COMPOSITIO HAVING EXTREME PRESSURE PROPERTIES COMPRISING A MAJOR AMOUNT OF AN OIL BASE MATERIAL AND FROM ABOUT 0.05 TO ABOUT 15.0% BY WEIGHT OF A COMPOUND HAVING THE FORMULA