CA1047506A - Sulphur containing lubricating oil additives - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
New compounds are derived from intra-molecular and inter-molecular, in the case of a polymer, sulphur bridges hydrocarbon rings containing from 6 to 12 carbon atoms. The hydrocarbon ring is preferably 1.5-cyclooctadiene.
The compounds also contain the residue of an alkyl, alkenyl or aralkyl xanthate and may also contain the residue of a further nucleophilic group. The new compounds are useful in lubricating oil compositions. The compositions may also contain other conventional lubricant additives.

Description

` . 1047S06 ~ he present invention relates to sulphur-containing lubricating oil additives.
According to the present invention there is provided an oil-soluble compound having the formula:

S A
A - R - S - ~ _ oRl or~R2~
I n (I) Rl - C- S

wherein in Formula (I) R is a sulfur-bridged hydrocarbon ring derived from 1,3,5-cycloheptatriene or 1,5~9-cyclododecatriene, said sulfur-bridge being a single sulfur bridge between two non-ad~acent carbon atcms of said ring forming a bicyclo compound and wherein in Formula (II) R2 is a polymer com-prising the residue of a plurality of n hydrocarbon rings which are derivedfrom 1,3,5-cycloheptatriene, cyclooctatetrene, 1,3-cyclooct~ene, 1,5-cyclo-octadiene, 3-alkoxy derivatives thereof and 1,5,9-cyclododecatriene, said n hy-drocarbon rings being connected through a sulfur bridge, n being the degree of polymerisation such that said compound is oil-soluble, R is the same or dif-ferent and is an alkyl, aIkenyl or aralkyl grouP and A is a nucleophyllic group selected from r s - LS_C_OR1~ , -CN,-NCS,-XH~-XR3, X X 3 X oR3 -X-~_R3,_X_c_N / R and -X-P /
\ R3 \ oR3 wherein Rl is as above, X is oxygen or sulfur and R3 is alkyl, aryl, aIkaryl or aralkyl.
The sulphur bridging in R and R is conveniently achieved by re-acting with sulphur dichloride or other sulphur chloride compound to yield either monomeric or polymeric derivatives. The sulphur bridges may be oxidised to carry one or two oxygens.
The group A preferably has the formula:-iO4'~506 (S - C~ oR13 wherein Rl is as defined above and wherein the two grouPs Rl may be the same or different.
The invention also includes a lubricating oil composition which com-prises a n~jor amount of a lubricating oil and a minor amount of compound as defined above. Such compositions m~y be employed directly as lubricants and the novel compoundsof the present invention are preferably present in an a-mount from 0.01 to 10% by weight, more particularly ~rom 0.5 to 3% by weight, although in a few cases, e.g. 2,6 bis(methoxythiocarbonylthio)-9-thiabicyclo ~3,3,1~ nonane, oil solubility may be somewhat li~ited. Thus the number of carbon atoms in the, or each, group Rl, and the, or each, group R3 if present, should be sufficiently high to render the compounds oil soluble. On the other hand it is desirable that the number of carbon atoms in the grouPs Rl and R3 should not be too high since it is believed that the sulphur in the molecule is the active component, and with high molecular weight large amounts of the compounds would have to be used to give equivalent sulphur contents. Partl-cularly preferred additives in this respect are compounds in which A is a group of the formula:-~ - C~ - OR~

and in which one group R is an ethyl or propyl grouP and the other grouP is a methyl, ethyl or propyl grouP-However, the term lubricating oil composition also embraces the ma-terials known in the art as oil concentrates and additive packages, i.e. con-centrated solutions in lubricating oil, optionally together with one or more conventional additives intended to be diluted with further , quantities of oil to form the final lubricant. In this case "
the novel compounds of the present invention m~y be present in a wide range of proportions e.g. 10% to 90%. In gener~l such concentrated solutions will normally contain from 20%
to 50% by weight of the novel compounds of the present invention. The lubricating oil used in the lubricants, or the concentrates or packages, may be any of the well known oils of appropr ate viscosity characteristics and may include synthetic oils.
The ~ulphur-bridged compounds may be prepared by reacting sulphur dichloride with the unsaturated ring compound preferably in an inert solvent at a temperature betwe-en -20 and 100C to give a dichloro derivative. Details of the preparations of these compounds are given in J. Org. Chem. 33, p. 2627 (196&);
~15 J Org. ~h~m. 31, p. 1679 and 1669 (1966).
:. The compounds of the present invention may then be prqpared by reàcting the metal, preferably sodium, or e~pecially potassium, salt of an alkyl, alkenyl or aralkyl xanthate with the d chloro sulphur-bridged compound, in the ratio of two moles of xanthate to one mole of dichloro sulphur-bridged compound when compounds of the formula:- R10 - C = S
` R r- s c - ORl~ or ~R ~n R10 - C = S
are oDt~ined wherein R, R , R and n have the same significance as above.
When the xanthate and the dicnloro sulphur-brid~ed - compound are reacted in a mole ratio of 1:1. one c~lorine remains unreacted. This chlorine atom is then reacted with me~al derivatives of the nucleophilic group A.
The invention therefore includes as ir.termediates 10~7506 compounds having the formulae Cl - R - S - ~ - ORl and ...... ..... ....... ...... rCl21 1 1 ~herein R, Rl and ~ X2~ ~have R 0 - C = S n the same significance as above.
Alternatively, the derivative of the nucleophilic group A may be reacted with the dichloro sulphur-bridged compound which may then be reacted with the xanthate.
In some cases, the compounds of the invention may possess residual reactive ethylenically unsaturated double bonds which may be reacted with compounds reactive therewith.
0 Such compounds reacting with residual unsaturation include sùlphur~ phosphorus pentasulphide, mercaptans, phenols, ~ thiocyana~e anions, thiophenols and carboxylic acids. Specific : examples of such compounds are mercaptans and carboxylic acids con~aining from 1 to 16 carbon atomR; phenol (unsubstituted) and thiophenol (unsubstituted). The~foregoing compounds may be - reacted with the residual unsàturation at a temperature of from 50 to 200C and in the case of sulphur, thiocyanates and phosphorus pentasulphide no catalyst is required; In the ` case of the other compounds, however, it may be desiràble to use a catalyst known to promote their reaction with ethylen-- ically unsaturated double bonds, such as mineral acids or Lewis acid catalysts such as boron trifluoride or the etherate - or phenolate complex thereof.
It will be understood that the lubricating compositions of the present invention may also contain, if desired, conventional lubricant additives such as ancillary antioxidants and antiwear additives (preferably ashless)~ corrosion inh~ibitors, dispersants, particularly dispersants of the succinimide type, detergents, thickeners, pour-point ~047S06 depressants and viscosity index improvers. Numerous examples of such conventional additives are described in U.K. Patent Specification No 1,205,177 and the various document3 referred to therein.
There now follows by way of example a description of the preparation of typica~ compounds in accordance with the present invention:
Example 1 Preparation of Intermediate A

2,6 dichloro-9-thiabicyclo ~3;3~ nonane Methylene chloride (1,250 ml~ wa~s stirred at a temperature between 0 and -5C in a glass vessel fitted with nitrogen inlet and dropping funnels. 1,5 cyclo-octadiene (1080 g, 10 mcles) and sulphur dichloride (103 g; 10 moles)'were added from the 15. dropping f~nnel~ at equivalent ~ates over 5~ hours whilst ',",' maintaining the cooling bath at'-25 to -30C. When the ad,ditio,n was complete the mixture was allowed to warm to room - t~mperature overnight and then'heate~ to 46 to 47C for two hours.
- The product was,precipitated~on cooling to below room temperature, filtered off and dried at 50C in vacuum ' ' oven to yield 1511 g (72%) of a product containing 31.9% Cl (calc. 33.7) and 16.4% S (calc. 15.1). The melting point, after recrystallisation, 92.5 - 93.5C, and infrared analysis , confirmed that the product was 2,6 dichloro-9-thiabicyclo t3,3,1~ nonane.
Preparation of 2,6-bis(butoxythiocarbonylthio) , -9-thiabicyclo ~,3,1~ nonane Commerc-al grade potassium hydroxide (66g; 1 mole) of 85% purity was dissolved in n-butanol (300g) by heating ra~idly to about 75C, then cooled rapidly to about 3~C
in a water bath. Carbon d~sulphide (76g; 1.0 moles) wa~ ~ddeQ

~047S06 dropwise over about 50 minutes and the temperature maintained below 40C by a water bath because of the gentle exotherm, during which time a bright yellow precipitate was formed. When . the addition was completed the temperature of the solution of potassium xanthate thus formed was heated to 50C and a solution of Intermediate A (105.5g; 0.5 moles) in toluene t400 ml) warmed to about 60C was added.
The mixture increased in viscosity and turned brown and was refluxed (about 91C) for 4 hours and then cooled to room temperature. After washing three times with 150 ml of water : . -....... an~ a.further.bhree.time with lO~.~ml o~ ~aterj-the mixture.was:
dried over magnesium sulphate, filtered and stripped on a rotary evaporator to 100C/20 torr. The residue was filtered through`glass-fibre paper on.a hea.ted funnel to yield a viscous li~ht brown liquid which solidified to a light yellow : solid on standing.
181g ~83%) of the protuct containing 35.8% S (calc. 36.6) ....... and 0.36% Cl was obtained, infrared ~nalysis confirming the structure . ' 7\ 11 S ~ S C - O.- CH2CH2CH2Ch3 CH3~.CH2~CH2~CH2~~C-S ~

. .
Exam~les 2 to 20 . Further compounds in accordance with the present invention were prepared in a ~ubstantially similar manner to that of Example 1, the details of the preparations and amounts 25 used being summarised in Table 1.
.Intermediate B was prepared in a similar manner to Int-ermediate A, except that the starting materials used were .cy~loaodecatriene (410g; 5 moles) sulphur dichloride (103g;
1.0 moles) ana 2.5 litres of metnylene dichloride, -xce~s iO47506 cyclododecatriene then being stripped off and the resulting material recrystallised from petroleum ether (b.pt. 62-68C).
Intermediate Bl was prepared in similar manner to . intermediate B, except that 6 moles cyclododecatriene and 1.2 moles sulphur dichloride were used.
Intermediate Al was prepared in a similar manner to Intermediate A, except that 1620g 1,5-cyclooctadiene and 1545g sulphur-dichloride were aaded over about 6~ hours to 1800 ml methylene chloride at 0C to -5C.

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104'~S06 xample_21 Preparation of Inte.mediate 2,6 - dichloro - 9 - thiabicyclo (3,3,1) nonane Sulphur dichloride (1030g. 10 m.) and 1,5-cyclooctadiene (1080g. 10 m.) were added simultaneously, at equal molar rates, to methylene dichloride (1250 ml.) maintained at 0 to -5C.
over a period of 4~ hours. The resulting mixture was allowed to wàrm to room temperature overnight, then heated to 45C. for 2 hours, cooled to room temperature and refrigerated to yield 1670.6g. (79.3%) of solid product which was filtered off and dried in a vacuum oven at 50C.
Analysis of product:- %S 14.86 (calc. 15.1) %Cl.31.7 (calc. 33.7) Preparation of 2,6-bis (methoxy/ethoxythiocarbonyl-. .
~hio)-9-thiabicyclo (3,3,1) nonane ~otassium hydroxide (72.2g. 1;1 m. of 85~ purity) was .. . .
added to a mixture of alcohols (ethanol 177g + methanol 123g.) and heated until dissolved. The re~ùlting mixture was cooled ,.,, ~
to about 45~C and carbon disulphide (84g. 1.1 m.) aaded while maintaining the reaction temperature at about 40C., where-after a solution of the intermediate prepared above (105.5~
0.5m. dissolved in 400 ml. toluene) was added over a period of 40 minutes during which the temperature was maintained in the range 40-50C. A yellow precipitate formed. m e reaction mixture was refluxed ~72C.) for 4 hours, then washed with water after addition of toluene to ensure phase separation and the organic layer separated. The organic layer was filtered, dried over anhydrous magnesium sulphate o~rernight, refiltered, stripped to 100C./20 torr and the residue refiltered to yield 106g. (57.6%) of the product as~a viscous red iiquid.
..

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104'7S06 Analysis of product:- 44.7%S ~calc. 43.5~) 0.65%Cl. (calc. 0) Example 22 2,6 -bis (~ethoxy/n - butoxythiocarbonylthio)-9-thiabicyclo (3,3,1) nonane The intermediate was prepared in similar manner to Example 21 from 940 ml. methylene dichloride, 774g. ~7.5 m.) sulphur dichloride and 810g. (7.5 m.j 1,5-cyclooctadiene Analysis 16 ~ 4%S ( calc. 15.1) 33.5%Cl. (calc. ~3.7) The product was prepared in similar manner to Example 21 from 36.1g. 85% purity potassium hydroxide, a mixture of 61.6g. methanol and 142.5g. n-butanoi, 42g. (0.55 m.) carbon disulph1de and 52.7g. (0.25 m. ) of inter~ediate dissolved in - 200 ml. to`luene; and the yield was 59.7g.
Analysis of product;- 39.2%S (calc. 40.4~) 0.6%Cl. (calc. 0) Example 23 The same product as in Example 22 was prepared in similar .
manner except in that the mixture ~of alcohols consisted of 31.4 methanol and 212g. n-butanol; and the yield was 80.lg.
Analysis of product:- 39.4%S ; (calc. 38.3%) 0 . 33%Cl . ( calc. 0) Example 24 2 - allyloxythiocarbonylthio 6 - isopropyloxythiocarbonylthio - _ - 9 - thiabicyclo (3,3,1) nonane The product was prepared in similar manner to Example 21 from potassium hydroxide (72. 5g. 1.1 m. 85% purity), a mixture of allyl alcohol (145g. 2.5 m.) isopropyl alcohol (150g.
2.5 m.), carbon disulphide (~3.6g. 1.1 m.) and 2,6-dichlorv-9-~hiabicyclo (3,3,1) nonane (105. 5g. 0. 5 m.) in 400 ml.
toluene; and the yield was 150g . ( 7 ~ . 5% ) .

104'75~)6 Analysis of product:- 37.5%S ~calc. 39.2) 0.35%Cl. (calc. 0.00) Example 25 2,6 bis (methoxy/ethoxythiocarbonylthio) - 9 - thiabicyclo (3 3 1) nonane -(a) Potassium hydroxide (36.1g. 0.55 m. 85% purity) was dissolved in ethanol (150 ml. 740P) by heating to 50C.
for 10 minutes. The solution was cooled to 40C. and carbon disulphide (41.8g. 0.55 m.) added over 20 minutes, toluene (50 ml.) being added to maintain stirring. A solution of 2,6-dichloro - 9 - thiabicyclo (3,3,1) nonane ~105.5g. 0.5 m.) in toluene (400 ml.) was added over 40 minutes with cooling. The temperature was allowed to rise under~the exotherm until a steady temperature was reached and the mixture then heated to " . . .
70C. for 4 hours. The product was allowed to cool and was filtered, two phases being present. After drying over magnesiur.
sulphate and filtration ~ne solvent was stripped off to yield p~oduct (a~. ~
(b) Potassium hydroxide (36.lg. 1.1 m. 85% purity) w-as dissolved in methanol (150 ml.) in a fresh glass vessel.
Carbon disulphide (41.8g. 0.55 m.) was added over ~ hour with stirring. Product (a) dissolved in toluene (40û ml.) was added over 3/4 hour and the mixture heated for 4 hours at 64C. After cooling the product was washed with three portions of water, toluene being ad~ed to aid separation. After drying over magnesium sulphate, filtering and stripping 150g.
(81.5%) of the above named product, a viscous orange liquid, was obtained.
Analysis of product:- 35.6%S (calc. 43.5%) 0.75%Cl. ~calc. O.OOi~) . .

~047506 Three further examples (Examples 26 to 28) were carr ed out in substantially the same manner as in Example 25, details only of the reactants and product analyse~ therefore being specified in each case.
Example 26 2,6 bis (methoxy/butoxythiocarbonylthio) - 9 - thia-bicyclo (3,3,1) nonane (a) KOH (72.2g. 1.1 m. 85% purity), n-butanol (400 ml.), CS2 (83.6g. 1.1 m.) 2,6 dichloro-9-thiabicyclo (3,3,1) nonane (211g. 1 m.) and toluene (800 ml.).
(b) KOH (72.2g. 1.1 m. 85% purity), methanol (300 ml.), CS2 (83.6g. 1.1 m.) and toluene (600 ml.). Reaction product of (a) added to (b). Yield of final product was 332.8g. (8470).
Analysis of product (orange liquid);-31.7%S (calc. 40.4) ~ . 0:~5%~1. (calc. 0.00) , ~ Example 27 2,6 bis(ethoxy/butoxythiocarbonylthio) - 9 - thiabicyclo (3,3;1) nonane (a) KOH (18g. 0.275 m. 85% purity) n-butanol (100 ml.) CS2 (21g. 0.275 m.) 2, 6 dichloro- 9 thia bicyclo (3~3,1) nonane ;.
(52.8g. 0.25 m.) toluene (200 ml.).

(b) KOH tl8g. 0.275 m. 85% purity) ethanol (lOO ml.) ~ CS2 (21g. 0.275 m.) toluene (200 ml.) Reaction product of (a) 25 - added to reaction product of (b). Yield of final product was 72.6g. ~71%).

Analysis of product:- 31.4%S ~calc. 39%) 0.5%Cl. (calc. 0.00) Example 28 2 - allyloxythiocarbonylthlo - 6 - isopropoxythiocarbonylthio _ - 9 - thiabicyclo (3,3~1) nonane (a) KOH (32.9g. 0.5 m. 85% purity), iso propyl alcohol (200 ml.) CS2 (38g. 0.5 m.) 2,6 - dichloro - 9 - thia bicyclo (3,3,1) nonane (105.5g. 0.5 m.) toluene (400 ml.) (b) KOH (39.5g. 0.6 m. 85% purity) allyl alcohol (150 ml.) CS2 (45.6g. 0.6 m.). Reaction product of (a) added to reaction product (b). Yield of final product was 176.4g. (86. 5% ) ~
Analysis of product:- 34.02%S (calc. 39. 2/o ) 0.41%Cl. (calc. 0.00%) Example 29 2-Dodecylthio-6-isopropoxythiocarbonylthio-9-thiabicyclo (3,3,1) nonane n-Dodecylmercaptan (50.5g. O. 25 m.) was dissolved by stirring in toluene (200 ml.j and then sodiun, metal (5.8g.
0.25 m. 3 added over 20 minutes at 100'C. After heating for 2 hours at~ 110C. a white suspe~sion was obtained which was ' added to a solution o~ 2,6-dlchloro-9-thia bicyclo (3,3,1) nonane (211g.-- 0.25 m.) in 'toluene (200 ml.) over 5 minutes - 'and subsequently heated to 100C. foF 3 hours, cooled and filtered through glass-fibre filter and added to a solution , . . , ..... j .
of potassium isopropyl'xanthate ir~ isopropyl alcohol.
The latter was prepared by dissolving potassium hydroxide (20g. 0.3 m. 85% purity) in isopropyl alcohol and adding carbon disulphide (22.8g. 0.3 m.) thereto whilst maintaining the -~- temperature at 38-40 C. The mixture was heated at 80C. for 3 hours, cooled, washed with water and dried over magnesium sulphate to yield 101.4g. (85.2%) of the desired product.-Analysis of product:- 26.1%S (calc. 26.9%) O.68%Cl. ~calc. 0.00,0) Examples 30 to 37 Further compounds in accor~ance with the present in~vention were prepared in a substantially similar manner to that of Example 29, details of the reactants and product _' _ _ -- ln47so6 . D g g O
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analyses being summarised in Table 2 in which, for convenience, 2,6-dichloro-9-thiabicyclo (3,3,1) nonane has been abbreviated to 2,6 DTN.
Example 38 2 (octanoxythiocarbonylthio) - 9 - cyano - 13 - thia-bicyclo (8,2,1) tridec - 5 - ene (a) Sodium cyanide (12,3g. 0.25 m.), ethanol (300 ml.
740P) and 2,9-dichloro - 13 - thia bicyclo (8,2,1) tridec-5-ene (66.3g. 0.25 m.) were mixed and the exothermic reaction allowed to proceed (35C.) for one hour then heated for 3 hours ~t 75C. After cooling water (600 ml.) was added to precipitate a product which was filtered off and dissolved in toluene.
(b) Potassium hydroxide (19.8g. 0.3 m. 85% purlty) was dissolved in n-octanol (200 ml.) by heating to 70C. for ~ hour.
After cooling to below 40~. .carbon disulphide (22.8g. 0.~ m.) was added ovér 20 minutes, a yellow precipitate being formed.
me toluene solution from (a) was added over 1 hour and the mixture heated to 9PC. for 3~ hours. On cooling the solution was washed three times with water (400 m:L. each)`, toluene .. ....
(400 ml.) being added to aid phase separation. The toluene solution was dried over magnesium sulphate and strip~ed on a rotary evaporator and then stripped under high vacuum from 70C. @ 0.1 Tprr to 120C. @ 0.2 Torr. The residue was a viscous brown liquid which appeared- to be the desired product.
Analysis of product:- 13.8%S ~calc. 22.6%) 0.94%Cl. ~calc. 0.00%) 3.05%~ (calc. 3.29h) Example 39 2 ethylhexyl xanthate of a polymer of 2,9-dichloro -3o 1 3 -thiabicyclo (8,~,1) tridec - 5 - ene Cis, trans, trans-cyclododeca - 1,5,9 - triene (324g.2m.) and sulphur dichloride (206g. 2 m.) were added simultaneously from two dropping funnels into stirred dichloromethane (1000 ml.) maintained at a temperature of O to -5C. Dy an acetone/dry ice bath at a rate of 2 vols to 1 vol respectively. The mixture was allowed to warm to room temperature over the weekend~
After heating to reflux (45C.) for 4 hours it was cooled in a refrigerator in order to attempt recrystallisation. Since no crystals were formed the solvent was removed on a rotary evaporator. On stirring with 62-68C. special boiling petroleum ether, 2,9-dichloro-13-thiabicyclo (8,2,1) -tridec-5-ene (DCTT) was dissolved leaving a light brown solid polymer also insoluble in toluene which was found to contain 12.7%S (calc.
12.07%) and 23.8%Cl. (Calc. 26.8%) which-figures correspond to a polymer of DCTT.
... ..
Potassium hydroxide (49.4g. 0.75 m. 85% purity) was .. . . . . . . .
dissolved in 2 ethyl hexanol (500 ml.) by heating to 90C. for ~ hour, c~oled to below 40C. and carbon disulphide (57g.
- 0.75 m.) added over 25 minutes, toluene (100 ml.) being added to maintain fIuidity. DCTT polymer (66.3g. 0.25 m.) in 2-ethyl nexanol (500 ml.) was ad~ed over 45 minutes. The solution was heated at 80-85C. for 4 hours, cooled, diluted with~
toluene (600 ml.), washed four times with water (400 mls. each) dried over magnesium sulphate and filtered. After removing the solvent on a rotary evaporator the product was stripped 25- under high vacuum to a base température of 80C. @ 0.1 Torr.
The product was found to contain 15.8%S (calc. 26.5%) and 1.06%Cl. (calc. 0.00%).
Example 40 Example 39 was repeated except that the reactants were added to the dichloromethane at a temperature of 20-30~ and then heated to 45C for 3 hours. The mixture was then extracted with hot petroleum ether (b.pt. 62-68C) ~047506 leaving a solid polymer found to contain 12.06%S and 28%Cl.
Thereafter a ~ubsequent reaction was carried out as described in Example 39 to yielu 80g. of product.
Analysis of product:- 25.1%S (calc 26.5%) 1.7i~Cl. (calc. 0.00%) Example 41 2,9-bis(crotyloxythiocarbonylthio)-13-thiabicyclo (8,2,1) tridec-5-ene Example 19 was repeated except in that Intermediate B (66.3g. 0.25 m.) wa~ used in place of Intermediate Al. Yield of product was 112g, (91.4%).
Analysis of product;- 30.5%S (calc. 32.7%) 1.27~Cl. (calc. O.00Z) Example 42 2,6-bis(isopropoxythiocarbonylthio)-8-thiabicyclo (3,2,1) . . ....... .. .. .
~ -oct-3-ene ., ~ .
1?3,5-Cycloheptatriene (184g, 2.0 m.) and sulphur dichloride (206g. 2.0 m.) each dissolved in 250 ml. methylene dichloride were added simultanëous~t equimolar rates to . ~ ..;
500 ml. methylene dichloride at -20C over 5 hours. The mixture was allowed to warm to room temperature overnight and the solvent stripped off on a rotary evaporator. The product was then distilled out of the residue ~rom the rotary .. . . .
evaporator.
` The intermediate prepared as in the preceding paragraph (114g. 0.58 m.) dissolved in 200 ml. toluene was added to 1.3 m. of potassium isopropyl xanthate and the mixture heated for 5 hours at 80 C. Further toluene was then added and the resulting solution washed with water and dried over MgS04. The toluene was then stripped off on a ~otary evaporator to yield 146.4g. (64.1%) of a black liquid.

~047506 Analysis of product:- 38%S (calc. 40.6%) 2.34%Cl. (calc. 0.00%) Tests A to R' Certain of the compounds described in the foregoing Examples were dissolved in lubricating oil (1% solutions) and tested in the extended Petter Wl test.
The tests were carried out for ~6 hours, using a Petter Wl Laboratory engine built and run according to the standard IP 176/69 procedure, except in that a sample of' the oil was not taken after 16 hours. The blends under test contained an ashless dispersant, an antiDxidant, a surfactant and a corrosion inhibitor.
The criterion ta~en was t~ ~ earing weight loss which was of the same order or lower,than the bearing weight "-'15 lo~s for zinc dialkyl di,thioph~;$'p ~ e.' ,:" ~ Examples 1 and 2 gave blackened bearings but when the blénd was retested with 0.0~% of benzotriazole the bearings had a normal colour.
, The products of Exa'~ples 4 and 5 gave particularly low 20 'bearing weight losses and gooà colour~bearings in the absence of benzotriazole.
The product of Example 3 was only soluble to the extent o~ 0.25S in mineral oil. ., - '' The results of these tests are given in Table 3. It can be seen that the results compare favourably with a blend containing a zinc dialkyl dithiophosphate and other ash containing additives.
, In addition Copper Strip tests were carried out in accordance with IP Test Method 154/69 except in that the tests were carried out at 120C using the test additive dissolved in 500 Solvent Neutral mineral oil in an amount suf~icient to give a product sulphur level of 0.15% by weight. In this way was 25.

1047SO~i ,, tested each of the products of Examples 1, 2, 4, 5, 7-13, 16, 19, 25, 28-36 and 39-41 all of which gave results of la or lb.
Furthermore, the novel additives of the present invention were also found to have useful load carrying properties.

`, .. . : , .

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~04~7S06 " TABLE ~
_ ._ TE~T BLEND CONTAINING BEARING WEIGHT COLOUR
1% of EXAMPLE No. LOSS (mg.) 8 , 2, 30 BLACK.

4 STRAW.
_ D 5 7 STRAW.
_ 7 17 STRAW.
_ .
F 12 8.1 BROWN TO DARK
. PATCHES.
G 13 16 LIGHT STRAW.
` DARK STRAW PATCHES.
14 14 STRAW. DARK STRAW
- PATCHES.
_ .
I 15 14 LIGHT STRAW, . PEACOCK COLOURS.
.
J- 16 53.3 DARK BROWN - BLACK
LACQUER.
_ K 17 22 - BROWN-PEACOCK.
L 28 (1.5%) 19 BROWN TRACES BLACK.
~ M ' 32 17 STRAW-PEACOCK.
N , 33 ~ 12;- BROWN TRABLACSKOF
_. ~ ., I
O 34 .1~. STRAW-PEACOCK
- p 35 12 STRAW-TRACES LACQUER. ¦
: 36 , 8 STRAW-PEACOCK.
_ 39 '20 LIGHT STRAW-COPPER/
R ; PEACOCK PATCHES.
... . . . ~ ~
., .
. ~. .
;.
.
. . ' ' , , - .

. .
, 27.

Claims (27)

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

1. An oil-soluble compound having the formula:

or (II) (I) wherein in Formula (I) R is a sulfur-bridged hydrocarbon ring derived from 1,3,5-cycloheptatriene or 1,5,9-cyclododecatriene, said sulfur-bridge being a single sulfur bridge between two non-adjacent carbon atoms of said ring forming a bicyclo compound and wherein in Formula (II) R2 is a polymer com-prising the residue of a plurality of n hydrocarbon rings which are derived from 1,3,5-cycloheptatriene, cyclooctatetrene, 1,3-cyclooctadiene, 1,5-cyclooctadiene, 3-alkoxy derivatives thereof and 1,5,9-cyclododecatriene, said n hydrocarbon rings being connected through a sulfur bridge, n being the degree of polymerization such that said compound is oil-soluble, R1 is the same or different and is an alkyl, alkenyl or aralkyl group and A is a nucleophyllic group selected from , -CN,-NCS,-XH,-XR3, , and wherein R1 is as above, X is oxygen or sulfur and R3 is alkyl, aryl, alkaryl or aralkyl.

2. The compound of claim 1 wherein each R1 is selected from the group consisting of alkyl and alkenyl groups containing from 1 to 20 carbon atoms.

3. The compound of claim 1 wherein the group A has the formula:

wherein R1 is as defined in claim 1 and wherein the two groups R1 may be the same or different.

4. The compound of claim 1 wherein the group A is selected from the group consisting of groups of the formula -CN and -NCS.

5. A compound of claim 1 having formula (I) wherein R is derived from 1,5,9-cyclododecatriene.

6. A compound of claim 5 wherein R1 is alkyl.

7. A compound of claim 6, namely 2,9-bis(butoxythiocarbonylthio)-13-thiabicyclo(8,2,1)tridec-5-ene.

8. A compound of claim 6, namely 2,9-bis(isopropoxythiocarbonylthio)-13-thiabicyclo(8,2,1)tridec-5-ene.

9. A compound of claim 6, namely 2,9-bis-(2-ethylhexanoxythiocarbonyl-thio)-13-thiabicyclo(8,2,1)tridec-5-ene.

10. A compound of claim 6, namely 2,9-bis-(1-methylbutoxythiocarbonyl-thio)-13-thiabicyclo(8,2,1)-tridec-5-ene.

11. A compound of claim 5, namely 2,9-bis(benzyloxythiocarbonylthio)-13-thiabicyclo(8,2,1)tridec-5-ene.

12. A compound of claim 1 having Formula I.

13. A lubricating composition comprising a major amount of a lubricating oil and a minor amount sufficient to improve the antioxidant properties of said oil of an oil-soluble compound of the formula or (I) (II) wherein in Formula (I) R is a sulfur-bridged hydrocarbon ring containing from 6-12 carbon atoms wherein said sulfur bridge is a single sulfur bridge between non-adjacent carbon atoms of said ring forming a bicyclo compound and wherein in Formula (II) R2 is a polymer comprising the residue of a plurality of n hydrocarbon rings containing from 6-12 carbon atoms, said n hydrocarbon rings being connected through a sulfur bridge, n being the degree of polymerization such that said compound is oil-soluble, each R1 is the same or different and is an alkyl, alkenyl or aralkyl group and A is a nucleophyllic group selected from , -CN, -NCS, -XH, -XR3, , and wherein R1 is as above, X is oxygen or sulfur and R3 is alkyl, aryl, alkaryl or aralkyl.

14. The lubricating composition of claim 13 containing from 0.01 to 10%
by weight of the compound of Formula (I) or (II).

15. The lubricating composition of claim 13 containing from 0.5 to 3%
by weight of the compound of Formula (I) or (II).

16. A lubricating composition of claim 13 wherein R and R2 are derived from an unsaturated ring compound selected from the group consisting of 1,3,5-cycloheptatriene, cyclooctatetrene,1,3-cyclooctadiene, 1,5-cyclooctadiene, and 1,5,9-cyclododecatriene.

17. A lubricating composition of claim 13 wherein said compound has the formula wherein R1 and A are as defined in claim 13.

18. A lubricating composition of claim 13 wherein said compound has the formula wherein R1 is as defined in claim 13.

19. A lubricating composition of claim 18 wherein said compound is 2,6-bis(butoxythiocarbonylthio)-9-thiabicyclo-(3,3,1)nonane.

20. A lubricating composition of claim 18 wherein said compound is 2,6-bis(ethoxythiocarbonylthio)-9-thiabicyclo-(3,3,1)nonane.

21. A lubricating composition of claim 18 wherein said compound is 2,6-bis(isopropoxythiocarbonylthio)-9-thiabicyclo(3,3,1)nonane.

22. A lubricating composition of claim 18 wherein said compound is 2,6-bis(benzyloxylthiocarbonylthio)-9-thiabicyclo(3,3,1)nonane.

23. A lubricating composition of claim 18 wherein said compound is 2,6-bis(2-ethylhexanoxythiocarbonylthio)-9-thiabicyclo(3,3,1)nonane.

24. A lubricating composition of claim 13 wherein said compound has the formula wherein R1 and A are as defined in claim 13.

25. A lubricating composition of claim 24 wherein said compound has the formula

26. A lubricating composition of claim 25 wherein said compound is 2,9-bis(butoxythiocarbonylthio)-13-thiabicyclo(8,2,1)tridec-5-ene.

27. A lubricating composition of claim 13 wherein said compound has Formula I.