NO750663L - - Google Patents

Description

The present invention relates to sulfur-containing lubricating oil additives.

According to the invention there is provided a compound of the formula

wherein formula (I) R is the residue of an intra-molecular sulfur-bridged hydrocarbon ring containing from 6 to 12 carbon atoms or wherein formula (II) is a polymer comprising the residue of several substantially inter-molecular sulfur-bridged hydrocarbon rings, each containing from 6 to 12 carbon atoms, where n is the degree of polyinerization, each R<1> being the same or different and being an alkyl or alkenyl group, preferably containing from 1 to 20, in particular from 2 to 8 carbon atoms, or an aralkyl group, preferably benzyl or alkylbenzyl, and where A is a nucleophilic group.

is preferably derived from monocyc-

sical olefins such as 1,3,5-cycloheptatriene, cyclooctatetraene, 1,3-cyclooctadiene-1,5-cyclooctadiene, or 3-alkoxy-

derivatives thereof, and the 1,5,9-cyclododecatriene especially the cis-trans-trans version thereof. The sulfur bridge in these hydrocarbons is obtained by reaction with sulfur dichloride or another sulfur chloride compound which gives either monomeric or polymeric derivatives. The sulfur bridges can be oxidized to carry one or two oxygen atoms.

Group A preferably has the formula

where R"*" is as stated above, and where the two groups R"<*>" can be the same or different. Alternatively, the group A can have the formula where X is oxygen or sulphur, and R<3> is an alkyl*, aryl, alkaryl or aralkyl group. Additional alternatives for A include -CN and -NCS. The invention also includes a lubricating oil composition comprising a lubricating oil and a compound as indicated above. Such compositions can be intended to be used directly as lubricants, in which case the new compounds according to the invention will be present in smaller amounts, preferably in an amount of from 0.01 to 10% by weight, in particular from 0.5 to 3 % by weight, although in a few cases, for example 2,6 bis(meth-oxythiocarbonylthio)-9-thiabicyclo[3,3,1Jnonane oil solubility may be somewhat limited. Thus, the number of carbon atoms in the or each group R"<*>", and the or each of the group R 3 if present, must be sufficiently high to make the compounds oil-soluble. On the other hand, it is on-1 3

important that the number of carbon atoms in the groups R and R x should not be too high, as it is assumed that the sulfur in the molecule is the active component, with the consequence that large amounts of the compounds must be used to give an equivalent sulfur content. Especially

preferred additives in this regard are compounds in which -A is a group of the formula

and in which group R<1> is an ethyl or propyl group and the other group is a methyl, ethyl or propyl group.

The term lubricating oil composition also includes materials known in the art as oil concentrates and additive packages, i.e. concentrated solutions in lubricating oil, possibly together with one or more conventional additives intended to be diluted with further amounts of oil to form the final lubricating agent. In this case, the new compounds according to the invention can be present within a certain quantity range, e.g. 10% to 90%. In general, such concentrated solutions will normally contain from 20 to 50% by weight of the new compounds according to the invention. The lubricating oil used in the lubricating agents, or concentrates or packs, can be any of the well-known oils with suitable viscosity characteristics, and can include synthetic oils.

The sulfur-bridged compounds can be prepared by reacting sulfur dichloride with the unsaturated ring compound, preferably in an inert solvent at a temperature between -20 and 100°C, forming a dichloro derivative. Details regarding the preparation of these compounds are given in J. Org. Chern. 33, page 2627 (1968); J. Org. Chem. 31, pages 1679 and 1669 (1966).

The compounds according to the present invention can then be prepared by reacting the metal salt, preferably sodium, or in particular potassium, of an alkyl, alkenyl or aralkyl xanthate with the dichlorosulfur-bridged compound in the ratio of two moles of xanthate to 1 mole of dichlorosulfur-bridged compound, where compounds of the formula

12

is obtained in which R, R , R and n have the previously indicated meanings.

When the xanthate and the dichlorosulfur bridged compound are reacted in a molar ratio of 1:1, chlorine remains unreacted. This chlorine atom is then reacted with metal derivatives of the nucleophilic group A.

The invention therefore includes, as intermediates, compounds of the formulas

1" 2l

where-R, R and |_ R J have: the previously stated meanings.

n

Alternatively, the derivative of the nucleophilic group A can be reacted with the dichlorosulfur bridged compound which can then be reacted with the xanthate.

In some cases, the compounds according to the invention can exhibit residual reactive ethylenically unsaturated double bonds which can be reacted with compounds which are reactive with these. Such compounds which react with rest saturation include sulfur, phosphorus pentasulfide, mercaptans, phenols, thiocyanate anions, thiophenols' and carboxylic acids. Specific examples of such compounds are mercaptans and carboxylic acids containing from 1 to 16 carbon atoms, phenol (unsubstituted) and thiophenol (unsubstituted). The preceding compounds can be reacted with the residual unsaturation at a temperature of from 50 to 200°C, and in the case of sulphur, thiocyanates and phosphorus pentasulphide, no catalyst is necessary. As regards the other compounds, however, it may be desirable to use a catalyst which is known to activate the reaction of these with the ethylenically unsaturated double bonds, such as mineral acids or Lewis acid catalysts such as boron trifluoride or the etberate or phenolate complex thereof.

It will be understood that the lubricant compositions according to the present invention can also contain, if desired, conventional lubricant additives such as auxiliary antioxidants and antiwear additives (preferably ash cellulose), corrosion inhibitors, dispersants, especially dispersants of the succinimide type, detergents, thickeners, pour point depressants and viscosity index improvers. Numerous examples of such conventional additives are described in British Patent Specification No. 1,205,177 and various publications cited therein.

The following examples illustrate the preparation of typical compounds according to the invention: Example 1 Preparation of intermediate product A

2, 6- dichloro- 9- thiabicyclo [3, 3, 1] nonane

1250 ml of methylene chloride was stirred at a temperature between 0 and -5°C in a shard of glass equipped with a nitrogen inlet and dropping funnel. 1080 g, (10 mol) 1.5 05/0 looctadiene and 103 g (10 mol) sulfur dichloride were added from the dropping funnels at an equal rate over 5 1/2 hours while the boiling bath was maintained at -25 - -30°C. When the addition was complete, the mixture was allowed to warm to room temperature overnight, and was then warmed to 46-47°C

in two hours. The product was precipitated by cooling to below room temperature, filtered off and dried at 50°C in vacuo to give 1511 g (72%)' of a product containing 31.9% Cl (calculated 33.7) and 16.3% S (calculated 15.1). Melting point after recrystallization was 92.5 - 93.5°C, and infrared analysis determined that the product was 2.6 dichloro-9-thiabicyclo[3,3, ljnonane.

Preparation of 2,6-bis(butoxythiocarbonylthio)

- 9-thiabicyclo[3,3,1]nonane

66 g (1 mol) potassium hydroxide of bandel quality with

85% purity was dissolved in 300 g of n-butanol by rapid heating to 75°C and was then rapidly cooled to approx. 35°C in a water bath. 76 g (1.0 mol) of carbon disulfide was added dropwise over 50 minutes, and the temperature was maintained below 40°C with a water bath due to the slight exothermic reaction, during which time a bright yellow precipitate formed. When the addition was complete, the temperature of the reading of the potassium xanthate thus formed was raised to 50°C, and a solution of 105.5 g (0.5 mol) of intermediate A in 400 ml of toluene heated to 60°C was added. The mixture increased in viscosity and turned brown and was refluxed (about 91°C) for 4 hours and then cooled to room temperature. After washing three times with 150 ml of water, and three more times with 100 ml of water, the mixture was dried over magnesium sulfate, filtered and stripped on a rotary evaporator at 100°C/20 torr. The residue was filtered through glass fiber paper on a heated funnel to give a viscous light brown liquid which solidified to a light yellow solid on standing. 181 g (83%) of the product containing 35.8% S (calcd. 36.6) and 0.36% Cl were obtained, and infrared analysis determined the structure

Examples 2-20

Further compounds according to the present invention were prepared essentially in the same way as in example 1, and details of the preparation and amounts used are listed in table 1.

Intermediate B was prepared in a similar manner to intermediate A, with the exception that the starting materials used were 410 g (5 mol) cyclododecatriene, 103 g (1.0 mol) sulfur dichloride and 2.5 liters of methylene dichloride, and the excess cyclododecatriene was then stripped of, and the resulting material recrystallized from petroleum ether (b.p. 62~68°C).

Intermediate B"^ was prepared in a similar manner to Intermediate B, with the exception that 6 moles of cyclododecatriene and 1.2 moles of sulfur dichloride were used.

Intermediate A was prepared in a similar manner to Intermediate A, with the exception that 1620 g of 1,5-cyclooctadiene and 1545 g of sulfur dichloride were added over 6 1/2 hours to 1800 ml of methylene chloride at 0 - -5°C.

Example 21 Preparation of intermediate 2, 6-dichloro-9-thiabicyclo (3, 3, 1) nonane

1030 g (10 mol) of sulfur dichloride and 100 g (10 mol) of 1,5-cyclooctadiene were added simultaneously at equal molar rates to 1050 ml of methylene dichloride held at 0 - -5°C over the course of 4 1/2 hours. The resulting mixture was allowed to warm to room temperature overnight, then heated to 45°C for 2 hours and cooled to room temperature and refrigerated to give 1670.6 g (79.3%) of a solid product which was filtered off and dried in vacuum at 50°C.

Analysis of product: % S 14.86 (calculated 15.1)

% Cl 31.7 (calcd. 33.7).

Preparation of 2,6-bis(methoxy/ethoxy-thiocarbonylthio)-9-thiabicyclo(3,3,1)nonane

72.2 g (1.1 mol) potassium hydroxide with 85% purity was added to a mixture of alcohols (177 g ethanol + 123 g methanol) and heated until dissolution. The resulting mixture was cooled to 40°C, and 84 g (1.1 mol) of carbon disulfide was added while maintaining the reaction temperature at ca. 40°C, after which a solution of 105.5 g (0.5 mol) of the intermediate product prepared above dissolved in 400 ml of toluene was added over the course of 40 minutes during which the temperature was kept in the range 40 - 50°C. A yellow precipitate was formed. The reaction mixture was refluxed (72°C) for 4 hours, then washed with water. after addition of toluene to ensure phase separation, and the organic layer was separated. The organic layer was filtered, dried over anhydrous magnesium sulfate overnight, filtered again, stripped at 100°C/20 torr, and the residue was filtered again to give 106 g (57.6%) of the product as a viscous, rod liquid.

Analysis of product: ' 44}. 7% S (calculated 43.5)

.0.65% Cl (calculated ') .

Example 22 2,6-bis(methoxy/n-butoxythiocarbony1-thio)-9- thiabicyclo (3,3,1)nonane The intermediate was prepared in a similar manner to

in example 21 from 940 ml methylene dichloride, 774 g (7.5 mol) sulfur dichloride and 810 g (7.5 mol) 1,5-cyclooctadiene.

Analysis: 16.4% S (calcd. 15.1)

33.5% Cl (calculated 33.7)

The product was prepared in a similar manner to Example 21 from 36.1 g potassium hydroxide of 85% purity, a mixture of 61.6 g methanol and 142.5 g n-butanol, 42 g (0.55 mol) carbon disulfide and 52, 7 g (0.25 mol) of the intermediate was dissolved in 200 ml of toluene, and the yield was 59.7 g.

Analysis of product: 39.2% S (calculated 40.4%)

0.6% Cl (calculated 0 )

Example 23

The same product as in Example 22 was prepared in a similar manner with the exception that the mixture of alcohols consisted of 31.4 g of methanol and 212 g of n-butanol, and the yield was 80.1 g.

Analysis of product: 39.4% S (calculated 38.3%)

0.33% Cl (calcd. 0 )

Example 24 2-allyloxythiocarbonylthio-6-isopropyl-oxythiocarbonylthio-9-thiabicyclo-

( 3, 3, 1) nonane

The product was prepared in a similar manner to Example 21 from 72.5 g (1.1 mol) potassium hydroxide of 85% purity, a mixture of 145 g (2.5 mol) allyl alcohol and 150 g (2.5 mol) isopropyl alcohol, 83.6 g (1.1 mol) of carbon disulfide and 105.5 g (0.5 mol) of 2,6-dichloro-9-thiabicyclo(3,3,1) nonane in 400 ml of toluene, and the yield was 150 g ( 73.5%).

Analysis of product: 37.5% S (calculated 39.2)

-0.35% Cl (calculated 0.0)

Example 25 2,6-bis(methoxy/ethoxythiocarbonylthio)-9-thiabicyclo(3,3,1)nonane

(a) 36.1 g (0.55 mol) of potassium hydroxide of 85% purity was

dissolved in 150 ml (740 P) ethanol by heating to 50°C for 10 minutes. The solution was cooled to 40°C, and 41.8 g (0.55 mol) of carbon disulfide was added over 20 minutes, adding 50 ml of toluene to maintain stirring. A solution of 105.5 g (Q.5 mol) of 2,6-dichloro-9-thiabicyclo(3,3,1) nonane in 400 ml of toluene was added over 40 minutes with cooling. The temperature was allowed to rise during the exothermic reaction until a steady temperature was reached, and the mixture was then heated to 70°C for 4 hours. The product was allowed to cool and was filtered, and where two phases were present. , After drying over magnesium sulfate and filtration, the solvent was stripped off to form product (a).

(b) 36.1 g (1.1 mol) of potassium hydroxide of 85% purity was obtained

dissolved in 150 ml of methanol in a clean glass shard. 41.8 g (0.55 mol) of carbon disulfide was added over 1/2 hour with stirring. Product (a) dissolved in 400 ml of toluene was added over 3/4 hour, and the mixture was heated for 4 hours at 64°C. After cooling, the product was washed with three portions of water, and toluene was added to accelerate separation. After drying over magnesium sulfate, filtering and stripping, 150 g (81.5%) of the above-mentioned product were obtained as a viscous, orange liquid.

Analysis of product: . 35.6% S (calculated 43.5%)

0.75% Cl (calculated 0.0%)

Three further examples (Examples 26 - 28) were carried out in substantially the same manner as in Example 25, and details of reactant and product analysis are therefore given specifically in each case.

Example 26 2,6 bis(methoxy/butoxytbiocarbonylthic)-9-thiabicyclo(3,3,1)nonane.

(a) 72.2 g (1.1 mol) KOH of 85% purity, 400 mL n-butanol, 83.6 g (1.1 mol) CS2, 211 g (1 mol) 2,6-dichloro -9-thiabicyclo (3,3,1) nonane and 800 ml of toluene. (b) 72.2 g (1.1 mol) KOH of 85% purity, 300 ml methanol, 83.6 g (1.1 mol) CSp°9600 ml toluene. The reaction product of (a) added to (b). The yield of the final product was 332.8 g (84%). Analysis of product (orange liquid): 31.7% S (calcd 40.4) 0.55% Cl (calcd 0.0) Example 27 2,6 bis(ethoxy/butoxythiocarbonylthio)-9- thiabicyclo (3, 3, 1) nonane (a) 18 g (0.275 mol) KOH of 85% purity, 100 ml n-butanol, 21 g. (0.275 mol) CS2, 52.8 g (0.25 mol) 2,6-dichloro-9 -thiabicyclo (3,3,1) nonane, 200 ml toluene. (b) 18 g (0.275 mol) KOH of 85% purity, 100 mL ethanol, 21 g (0.275 mol) CS 2 , 200 mL toluene. The reaction product of (a) added to the reaction product of (b). The yield of the final product was 72.6 g (71%).

Analysis of product: 31.4% S (calculated "39% )

0.5% Cl (calcd. 0.00)

Example 28 2-allyloxythiocarbonylthio~6-isopropoxythiocarbonylthio- 9- thiabicyclo ( 3, 3, 1 ) nonane (a) 32.9 g (0.5 mol) KOH of 85% purity, 200 ml isopropyl alcohol, 38 g (0.5 mol) CS2, 105.5 g (0.5 mol) 2,6-dichloro-9-thiabicyclo(3,3,1)nonane, 400 mL toluene. (b) 39.5 g (0.6 mol) KOH of 85% purity, 150 ml allyl alcohol hol, 45.6 g (0.6 mol) CS2 The reaction product of (a) added to the reaction product of (b). Yield of the final product was 176.4 g ((6.5%).

Analysis of product: 34.02% S (calculated 39.2%)

0.41% Cl (calculated 0.00%)

Example 29 2-dodecylthio-6-isopropoxythiocarbony1-thio-9-thiabicyclo (3,3,1)nonane

50.5 g (0.25 mol) of n-dodecyl mercaptan was dissolved by stirring in 200 ml of toluene, after which 5.8 g (0.25 mol) of sodium metal was added to the batch. of 20 minutes at 100°C. After heating for 2 hours at 110°C, a white suspension was obtained which was added to a solution of 211 g (0.25 mol) of 2,6-dichloro-9-thiabicyclo(3,3,1)nonane in 200 ml of toluene in run off for 5 minutes and then heated to 100°C for 3 hours, cooled and filtered through a glass fiber filter and added to a solution of potassium isopropyl xanthal in isopropyl alcohol.

The latter was prepared by dissolving 20 g (0.3 mol) potassium hydroxide of 85% purity in isopropyl alcohol,

<■ after which 22.8 g (0.3 mol) of carbon disulphide were added while the temperature was maintained at 38 - 40°C. The mixture was heated to 80°C for 3 hours, cooled, washed with water and dried over magnesium sulfate to give 101.4 g (85.2%) of the desired product.

Analysis of product: 26.1% S (calculated 26.9%)

0.68% Cl (calculated 0.00%)

Examples 30-37

Further compounds according to the present invention were prepared essentially in the same manner as in Example 29, and where details with regard to reactants and product analyzes are listed in Table 2 in which in which for the sake of brevity 2,6-dichloro-9-thiabicyclo (3,3 ,l)non to 2.6 DTN.

Example 38 2-(octanoxythiocarbonylthio)-9-cyano-13-thiabicyclo (8,2,1)tridec-5-ene (a) 12.3 g (0.25 mol) sodium cyanide, 300 ml (740 P) ethane ol and 66.3 g (0.25 mol) of 2,9-dichloro-13-thiabicyclo-(8,2,1)tridec-5-ene were mixed, and the exothermic reaction was allowed to proceed (35°C) for 1 hour, after which the mixture was heated for 3 hours at 75°C. After cooling, 600 ml of water was added to precipitate a product which was filtered off and dissolved in toluene. (b) 19.8 g (0.3 mol) of potassium hydroxide of 85% purity was recovered dissolved in 200 ml of n-octanol by heating to 70°C for 1/2 hour. After cooling to below 40°C, 22.8 g (0.3 mol) of carbon disulphide were added over the course of 20 minutes, whereby a yellow precipitate was formed. The toluene solution from (a) was added over 1 hour and the mixture was heated to 90°C for 3 hours. On cooling, the solution was washed three times with water (400 ml each time), after which 400 ml toluene was added to aid phase separation. The toluene solution was dried over magnesium sulfate and stripped on a rotary evaporator and then stripped under high vacuum from 70°C & 0.1 Torr to 120°C @ 0.2 Torr. The residue was a viscous brown liquid which appeared to be the desired product.

Analysis, of product: 13.8% S (calcd. 22.6%)

0.94% Cl (calculated 0.00%)

3.05% N (calculated 3.29%)

Example 39 2-ethylhexylxanthate of a polymer of 2,9-dichloro-13-thiabicyclo (8,2,1)tridec-5-ene

324 g (2 mol) of cis, trans, trans-cyclododeca-1,5,9-triene and 206 g (2 mol) of sulfur dichloride were added simultaneously from two dropping funnels into 1000 ml of stirred dichloromethane maintained at a temperature of 0 - -5° C using an acetone-dry ice bath at a rate of 2 volumes to 1 volume respectively. The mixture was allowed to warm to room temperature over the weekend. After heating to reflux (45°C) for 4 hours, the mixture was cooled in a fume hood to accelerate recrystallization. When no crystals formed, the solvent was removed on a rotary evaporator.

On stirring a 62 - 68°C special boiling petroleum ether, 2, 9-dichloro-13-thiabicyclo (8., 2, 1) -t.ridec-5-ene (DCTT) was dissolved and left a light brown solid polymer which was also insoluble in toluene, which was found to contain 12.7% S (calcd. 12.07%) and 23.8% Cl (calcd. 26.8%), corresponding to a polymer of

DCTT.

49.4 g (0.75 mol) of potassium hydroxide of 85% purity was dissolved in 500 ml of 2-ethylhexanol by heating to 90°C for 1/2 hour, cooled to below 40°C, after which 57 g (0.75 mol ) carbon disulphide was added over the course of 25 minutes, and to which 100 ml of toluene was added to maintain fluidity. 66.3 g (0.25 mol) of DCTT polymer in 500 ml of 2-ethylhexanol was added over 45 minutes. The solution was heated to 80-85°C for 4 hours, was cooled, diluted with 600 ml of toluene, washed four times with water (400 ml each time), dried over magnesium sulfate and filtered. After removal of the solvent on a rotary evaporator, the product was stripped under high vacuum to a temperature of 80°C @ 0.1 Torr. The product was found to contain 15.8% S (calculated 26.5%) and 1.06% Cl (calculated 0.00%).

Example 40

Example 39 was repeated with the exception that the reactants were added to the dichloromethane at a temperature of 20-30°C and then heated to 45°C for 3 hours. The mixture was then extracted with hot petroleum ether (b.p. 62 - 68°C) which gave a solid polymer which was found to contain 12.06% S and 28% Cio Then a subsequent reaction was carried out as described in Example 39 to form 80 g product.

Analysis of product: 25.1% S (calculated 26.5%)

1.71% Cl (calculated 0.00%)

Example 41 2,9-bis(crotyloxythiocarbonylIthio)-13-thiabicyclo (8,2,1)tridec-5-ene

Example 19 was repeated with the exception that 66.3 g (0.25 mol) of intermediate B^ was used instead of intermediate A<1>. Yield of product was 112 g (91.4%).

Analysis of product: 30.5% S (calculated 32.7%)

1.27% Cl. (calculated 0.00%)

Example 42 2,6-bis(isopropoxythiocarbonylthio)-8-thiabicyclo (3,2,1)oct-3-ene

184 g (2.0 mol) of 1,3,5-cycloheptatriene and 206 g (2.0 mol) of sulfur dichloride each dissolved in 250 ml of methylene dichloride were added simultaneously at equimolar rates to 500 ml of methylene dichloride at -20°C in the batch of 5 hours. The mixture was allowed to warm to room temperature overnight and the solvent was removed on a rotary evaporator. The product was then distilled from the residue on the rotary evaporator.

114 g (0.58 mol) intermediate product prepared as in the previous section dissolved in 200 ml toluene was added to 1.3 mol

potassium isopropyl xanthate, and the mixture was heated for 5 hours at 80°C. Additional toluene was then added and the resulting solution washed with water and dried over MgSO 4 . The toluene was then removed on a rotary evaporator to give 146.4 g (64.1%) of a black liquid.

Analysis of product: 38% S (calculated 40.6%)

2.34% Cl (calculated 0.00%)

Testing. A to R

Some of the compounds described in the preceding examples were dissolved in lubricating oil (1% solutions) and tested in the extended Petter Wl test.

The tests were carried out for 36 hours using a Petter Wl laboratory engine constructed and operated according to standard IP 176/69 procedure, with the exception that a sample of the oil was not taken after 16 hours. The tested mixtures contained an ash-free dispersant, an antioxidant, a surface-active agent and a corrosion inhibitor. The chosen criterion was the storage weight loss, which was of the same order of magnitude or lower than the storage weight loss with zinc dialkyldithiophosphate.

Examples 1 and 2 gave black deposits, however, when the mixture was retested with 0.01% benzotriazole. the bearings had a normal color.

The products according to examples 4 and 5 gave particularly low stock weight losses and good color on the stocks in the absence of benzotriazole.

The product according to example 3 was only soluble to an extent of 0.25% in mineral oil.

The results of these tests are listed in table 3. It appears that the results stand out favorably in relation to a mixture containing a zinc dialkyldithiophosphate and other ash-containing additives.

In addition, "Copper Strip" tests were carried out according to IP Test Method 154/69 except that the tests were carried out at 120°C using the test additive dissolved in 500 "Solvent Neutral" mineral oil in an amount sufficient to give a product sulfur content of 0, 15% by weight. In this way, each of the products according to examples 1, 2, 4, 5, 7-13, 16, 19, 25, 28-36 and 39-41 was tested, all of which gave results of la or lb.

Furthermore, the new additives according to the present invention were also found to have useful load-bearing properties.

Claims (46)

3-. Compound of formula: where in formula (I) R is the residue of an intramolecular sulfur bro-a hydrocarbon ring containing from 6 to 12 carbon atoms or where in formula (II) is a polymer comprising the residue of several essentially intra-molecular sulfur-bridged hydrocarbon rings, each containing from 6 to 12 carbon atoms, where n is the degree of polymerization, and where R is the same or different and is an alkyl, alkenyl or aralkyl group, and where A is a nucleophile group. 2. Compound according to claim 1, characterized in that each R is an alkyl or alkenyl group containing from 2 to 8 carbon atoms. 3. Compound according to claim 1 or 2, characterized in that R or is derived from 1,3,5-cycloheptatriene, cyclooctatetraene, 1,3-cyclooctadiene, 1,5-cyclooctadiene or a 3-alkyl derivative thereof, or cis, trans, trans-1,5,9-cyclododecatriene 4. Compound according to any one of claims 1-3, characterized in that the group A has the formula: where R^" is as previously indicated and where the two groups R"^ can be the same or different. 5. Compound according to claim 4, characterized in that one group R is an ethyl or propyl group and the other group R" is a ethyl, ethyl or propyl group. 6. Compound according to any one of claims 1-3, characterized in that the group A has the formula: where X is oxygen or sulphur, and R 3 is an alkyl, aryl, alkaryl or aralkyl groupi 7. Compound according to any one of claims 1-3, characterized in that the group A is -CN or -NCS. 8. 2,6-bis(butoxythiocarbonylthio)-9-thiabicyclo(3,3,1)-nonane. 9. 2,9-bis(butoxythiocarbonylthio)-13-thiabicyclo(8,2,1)-tridec-5-ene. 10. 2,6-bis(methoxythiocarbonylthio)-9-thiabicyclo(3,3,1)-nonane. 11. 2,6-bis(benzyloxythiocarbonylthio)-(3,3,1)nonane. 12. 2,6-bis(ethoxythiocarbonylthio)-9-thiabicyclo(3,3,1)-nonane. 13 . 2, 6-bis(isopropoxythiocarbonylthio)-9-thia.bicyclo-(3,3,1)nonane. . 14. 2,'9-bis(isopropoxythiocarbonylthio)-13-thiabicyclo-(8,2,1)tridec-5-ene. 15. 2,9-bis(2-ethylhexanoxythiocarbonylthio)-13-thiabicyclo(3,3,1)tridec-5-ene. 16. 2,9-bis(1-methylbutoxythiocarbonylthio)-13-thiabicyclo^,2,1)tridec-5-ene. 17. 2,9-bis(benzyloxythiocarbonylthio)-13-thiabicyclo-(8,2,1)tridec-5-ene. 18. 2,6-bis(n-propoxythiocarbonylthio)-thiabicyclo(3,3,1)-nonane. 19. 2,6-bis(1-methylpropoxythiocarbonylthio)-9-thiabicyclo-(3,3,1)nonane. 20. 2,6-bis(1-methylbutoxythiocarbonylthio)-9-thiabicyclo-(3,3,1)nonane.. 21. 2,6-bis(1-ethylpropoxythiocarbonylthio)-9-thiabicyclo-(3,3,1)nonane. 22. 2,6-bis(2-ethylhexanoxythiocarbonylthio)-9-thiabicyclo-(3,3,1)nonane. 23. 2,6-bis(tridecanoxythiocarbonylthio)-9-thiabicyclo-(3,3,1)nonane. 24. 2,6-bis(allyloxythiocarbonylthio)-9-thiabicyclo-(3,3,1)nonane. 25. 2,6-bis(crotyloxythiocarbonylthio)-9-thiabicyclo-(3,3,1)nonane. 26. 2,6-bis(cyclohexyloxythiocarbonylthio)-9-thiabicyclo-(3,3,1)nonane. 27. 2,6-bis(methoxy/ethoxythiocarbonylthio)-9-thiabicyclo-(3,3,1)nonane. 28. 2,6-bis(methoxy/n-butoxythiocarbonylthio)-9-thiabicyclo (3, 3, 1) nonane. 29. 2-allyloxythiocarbonylthio-6-isopropylthiocarbonylthio-9-thiabicyclo(3,3,1)nonane. 30. 2,6-bis(ethoxy/butoxythiocarbonylthio)-9-thiabicyclo-(3,3,1)nonane. 31. 2-(diisobutyl)dithiophosphato-6-isopropoxythiocarbony1-thio-9-thiabicyclo(3,3,1)nonane. 32. 2-(N,N-dibutylthiocarbamylthio)-6-(isopropoxythiocarbonylthio-9-thiabicyclo) (3,3,1)nonane. 33. 2-(butoxythiocarbonylthio)-6-phenoxy-9-thiabicyclo-(3,3,1)nonane. 34. 2-(butoxythiocarbonylthio)-6-(o-t-buty1-p-methylphenoxy-9-thiabicyclo (3,3,1) nonane. 35. 2-(isopropoxythiocarbonylthio)-6-(o-t-buty1-p-methyl-phenoxy-9-thiabicyclo (3,3,1) nonane. 36. 2-(butoxythiocarbonylthio)-6-(2,6-di-t-buty1-p-methyl-phenoxy)-9-thiabicyclo (3,3,1)nonane. 37. 2-(octanoxythiocarbonylthio)-6-isothiocyanato-9-thiabicyclo (3,3,1)nonane. 38. 2-(Hexanoxythiocarbonylthio)-6-isothiocyana to-9-thiabicyclo (3,3,1)nonane. 39. 2-(octanoxythiocarbonylthio)-9-cyano-13-thiabicyclo- v (8,2,1)tridec-5-ene. 40. 2,9-bis(crotyloxythiocarbonylthio)-13-thiabicyclo-(8,2,1)tridec-5-ene. 41. 2,6-bis(isopropoxythiocarbonylthio)-8-thiabicyclo-(3,2,1)oct-3-ene. 42. Process for the production of a new compound, characterized in that an alkyl-, alkenyl- or ar-alkylxanthate, or metal salt thereof, is reacted in a 2:1 molar ratio with a dichlorosulfur-bridged compound of the formula to form a compound of the formula 1 2 wherein R, R , R and n are as stated in claim 1. 43. Process for the production of a new compound, characterized in that an alkyl, alkenyl or aralkyl xanthate, or metal salt thereof, is reacted in a 1:1 molar ratio with a dichlorosulphur-bridged compound of formula: during the formation of an intermediate product, which is then converted into a 1:1 molar ratio with a metal salt of a nucleophilic group to form a compound of the formula: 1 2 where A, R, R , R and n are as stated in claim 1. 44. Method for the production of a new compound, characterized in that a metal salt of a nucleophilic group is reacted in a 1:1 molar ratio with a dichlorosulphur-bridged compound of formula: forming an intermediate which is then reacted in a 1:1 molar ratio with an alkyl, alkenyl or aralkyl xanthate, or metal salt thereof, to form a compound of the formula: 1 2 where A, R, R , R ' and n are as stated in claim 1. 45. Lubricant composition comprising a lubricating oil and an additive, characterized in that the additive is a compound of formula: where. in formula (I) R is the residue of an intramolecular sulfur-bridged hydrocarbon ring containing from 6 to 12 carbon atoms, or where in formula (II) is a polymer comprising the residue of several essentially inter-molecular sulfur-bridged hydrocarbon rings, each containing from 6 to 12 carbon atoms, where n is the degree of polymerization, each R"*" being the same or different and being an alkyl, alkenyl or aralkyl group, and A is a nucleophilic group. 46. Lubricant composition according to claim 45, characterized in that the compound of formula (I) or (II) is a compound according to any one of claims 2 to 41.