DE2508623A1 - SULFUR-CONTAINING LUBRICATING OIL ADDITIVES - Google Patents

Description

DR. BERG DIPL.-ING. STAPF DIPL.-ING. SCHWABE DR. DR. SANDMAIR

PATENTANWÄLTE 8 MÜNCHEN 86, POSTFACH 8602 45

Dr Berg Dipl.-Ing. Stapfund Partner, 8 Munich 86, P.O. Box 860245

Attorney's File No. 25 837

Your sign
Your ref.

Our sign

^Ourref 25 837

8 MUNICH 80

8 MUNCHbN 8Ü rt -7 _ "^

Mauerkircherstraße45 C (, f £ \ j ] J / ·)

Edwin Cooper and Company Ltd. Brackneil, Berkshire / Great Britain

Sulfur-containing lubricating oil additives

The invention relates to sulfur-containing lubricating oil additives.

According to the invention, compounds of the formulas

L · "Y ⁿ S

ARSC- OR " ¹ " or RO -C = S

(D

(ID

created, wherein in formula (I) R is the remainder of an intramolecular, sulfur-bridged hydrocarbon

V / bu - 2 -

, 0891988272 Telegrams BERGSTAPFPATENT Munich Banks: Bayerische Vereinsbank Munich 453 100

98> 043 TELEX: 0524560BERGd Hypo-Bank Munich 3892623

509836/0989 postal check Munich 65343-808

98 3310

- 2- 2508823

Substance ring with 6-12 carbon atoms or in which in formula (II) -J-R -j- is a polymer which is composed of the remainder of several consists essentially of intermolecular sulfur bridged hydrocarbon rings, each of which consists of 6-12 Has carbon atoms, η is the degree of polymerization, each R radical is identical or different and is an alkyl or alkenyl radical, preferably with 1-20, more preferably 2-8 carbon atoms, or an aralkyl radical, preferably benzyl or alkylbenzyl radical and A is a nucleophilic residue.

R and + -R -4- are preferably derived from monocyclic ones Olefins such as 1,3,5-cycloheptatriene, cyclooctatetraene, 1,3-cyclooctadiene, 1,5-cyclooctadiene or 3-alkoxy derivatives thereof and 1,5,9-cyclododecatriene, especially the cis-trans-trans version thereof. The sulfur bridge this hydrocarbon is obtained by treating with sulfur dichloride or another sulfur chloride compound is reacted to obtain either monomeric or polymeric derivatives. The sulfur bridges can be oxidized so that they contain an oxygen or two.

The radical A preferably has the formula:

S.
S - c ^y - OR ¹

in which R has the above meaning and in which the two R radicals can be identical or different. If necessary, can the remainder A have the following formulas:

509836/0989

-XH, -XR ³ , -XC-R ³ , -XCN ₁ "or -XP-OR ³ XX _R 3

3 wherein X is oxygen or sulfur and R is an alkyl , aryl, alkaryl or aralkyl radical. Other alternatives for A are -CN and -NCS.

The invention also includes a lubricating oil cover made of a lubricating oil and one defined above Connection exists. Such preparations can be intended to be used directly as lubricants will. In this case, the new compounds according to the invention are present in smaller amounts, preferably in one Amount of 0.01 to 10% by weight, especially 0.5 to 3% by weight, although in some cases, for example at 2,6 bis (methoxythiocarbonylthio) -9-thiabicyclo [3,3, IJ nonane, the oil solubility can be somewhat limited. Therefore, the number of carbon atoms in the or should be in each R residue and in the or in each R residue - if present - be sufficiently high to make the compounds oil-soluble close. On the other hand, it is desirable that the number of carbon atoms in the R groups and R residues is not too high, since it is assumed that the sulfur in the molecule is the effective component, otherwise large amounts of the compounds have to be used in order to obtain equivalent sulfur contents. Particularly preferred additives are in this regard

50983S / 0989

Compounds in which A is a radical of the formula

/ 7 , ι
SC - OR ^X j

and in which one R radical is an ethyl or propyl radical and the other radical is a methyl, ethyl or propyl radical is.

The term lubricating oil preparation also includes those skilled in the art as oil concentrates and additive packs Materials such as concentrated solutions in lubricating oil, possibly with one or more conventional additives, the are designed to be diluted with additional amounts of oil to form the final lubricant. In In this case, the new compounds according to the invention can be present in a wide range of amounts, for example in proportions of 10 - 90%. In general, such concentrated solutions usually contain 20-50% by weight of the new compounds according to the invention. The lubricating oil or the Concentrates or packages can be any of the well known oils with suitable viscosity characteristics and can be synthetic oils.

The sulfur bridged compounds can be made by adding sulfur dichloride to the unsaturated ring compound preferably in an inert solvent at a temperature of -2O to

609836/0989

+ 100 C is implemented to obtain a dichloro derivative. The details of making these compounds are given in the Journal Organ. Chem. 33 (1968) p. 2627 and 31 (1966) pp. 1679 and 1669.

The compounds of the invention can then be prepared are by adding the metal salt, preferably the sodium salt or, in particular, the potassium salt of an alkyl, alkenyl or aralkylxanthates with the sulfur bridged dichloro compound in a ratio of 2 moles of xanthate to 1 mole of sulfur bridged dichloro compound is converted if the compounds of the formulas

R ¹ O -C = S

Il

■ Ί

-S-C- OR U or,

R ¹ O -C = S

1 2
are obtained, wherein R, R, R and d have the above meaning.

If the xanthate and the sulfur bridged dichloro compound are reacted in a molar ratio of 1: 1, a chlorine remains unreacted. This chlorine atom is then mixed with metal derivatives of the nucleophilic radical A implemented.

509836/0989

The invention therefore includes interconnections

"1 the formulas Cl-R-S-C-OR and Cl

1 ι
RO -C = S

a, wherein R, R and -f-R J- have the above meaning.

The derivative of the nucleophilic radical A can optionally be reacted with the sulfur-bridged dichloro compound, which can then be reacted with the xanthate.

In some cases, the compounds according to the invention can have residual reactive ethylenically unsaturated double bonds which can be reacted with compounds reactive therewith. Such compounds that react with residual unsaturation are sulfur, phosphorus pentasulfide, mercaptans, phenols, thiocyanate anions, thiophenols and carboxylic acids. Specific examples of such compounds are mercaptans and carboxylic acids with 1-16 carbon atoms, (unsubstituted) phenol and (unsubstituted) thiophenol. The above compounds can with the residual unsaturation at a temperature from 50 to 200 ⁰ C are reacted and in the case of sulfur, thiocyanates and phosphorus pentasulfide no catalyst is required. In the case of the other

Connections, however, it may be desirable to have one

509836/0989

To use a catalyst which is known to promote their reaction with ethylenically unsaturated double bonds, such as mineral acids or Lewis acid catalysts, such as boron trifluoride or the etherate or phenolate complex of that.

It goes without saying that the lubricant formulations of the present invention also, if desired may contain conventional lubricant additives, such as additional antioxidants and anti-abrasion additives (preferably ashless), corrosion inhibitors, dispersants, in particular dispersants of the succinimide type, detergents, thickeners, pour point depressants and viscosity index improvers. Numerous examples of such conventional additives are given in British Patent Application 1 205 177, which also refers to other references.

The following examples illustrate the invention. example 1

Preparation of the intermediate product A 2, e-dichloro-g-thiabicyclo [3 _f 3, lj nonane methylene chloride (1.250 ml) was stirred at a temperature between 0 and -5 ° C. in a glass vessel equipped with a nitrogen inlet and a dropping funnel. 1,5-Cyclooctadiene (1080 g; 10 moles) and sulfur dichloride (103 g; 10 moles) were added from the dropping funnel within 5 1/2

509836/0989

Hours added at constant speed while the cooling bath was kept at -25 to -3O ° C. After the addition was complete, the mixture was allowed to warm to room temperature overnight and then Heated to 46 to 47 ° C for 2 hours.

The product was precipitated on cooling to room temperature, filtered off and stored at 50 ° C. in a vacuum drying cabinet dried and 1511 g (72%) of a product obtained which contains 31.9% Cl (calculated 33.7%) and 16.4% S (calculated 15.1%). After recrystallization the melting point was 92.5 to 93.5 C and the IR analysis showed that the product 2,6-dichloro-9-thiabicyclo (3,3, lj nonane was.

Production of 2,6-bis (butoxythiocarbonylthio) -9-thiabicyclo L3,3,1j nonane

Commercially available potassium hydroxide (66 g; 1 mol) with 85% purity was dissolved in n-butanol (300 g) by in quickly heated to about 75 ° C in a water bath and then rapidly cooled to about 35 ° C. Carbon disulfide (76 g; 1.0 mole) was added dropwise over a period of about 50 minutes and the Temperature kept below 40 ° C by a water bath because of the slightly exothermic reaction. During this Time a light yellow precipitate was formed. After the addition was complete, the temperature of the thus obtained

509836/0989

Tenen potassium xanthate solution heated to 50 ° C and a solution of intermediate A (105.5 g; 0.5 mol) in Toluene (400 ml) warmed to about 60 ° C was added.

The viscosity of the mixture increased and the mixture turned brown and refluxed for 4 hours (to about 91 ° C) and then cooled to room temperature. After washing 3 times with 150 ml Water and a further 3 washings with 100 ml of water, the mixture was dried over magnesium sulfate, filtered off and stripped on a rotary evaporator at 100 ° C / 2O Torr. The residue was through Filtered fiberglass paper on a heated funnel and obtained a slightly brown viscous liquid which solidified to a slightly yellow solid on standing.

181 g (83%) of the product containing 35.8% sulfur (calculated 36.6%) and 0.36% chlorine were obtained. The IR analysis confirmed the structure

/ Vs-c-0-

CH ₂ -CH ₂ CH ₂ CH ₃

- 10 -

509836/0989

Examples 2 to 20

Further compounds of the invention were essentially prepared in the same manner as described in Example 1. The details of the fabrications and the amounts used are summarized in Table I.

Intermediate B was prepared in the same manner as Intermediate A except that the starting materials used cyclododecytriene (41O g; 5 mol), sulfur dichloride (103 g? 1, O mol) and 2.5 liters of methylene dichloride were. The excess Cyclododecatriene was then stripped off and the material obtained from petroleum ether (boiling point: 62 - 68 ° CJ recrystallized.

Intermediate B was prepared in the same manner as Intermediate B except that 6 moles of cyclododecatriene and 1.2 moles of sulfur dichloride were used.

Intermediate A was prepared in the same way as the intermediate A produced with the exception that 1620 g of 1,5-cyclooctadiene and 1545 g of sulfur dichloride to 1800 ml of methylene chloride at 0 ° C to -5 ° C over a period of about 6 1/2 hours.

- 11 -

509836/0989

Table I.

on O CO 00 to σ> ■ ^.

ίθ SO

at
game product Between
product G 106 Mole alcohol lot 2 2,9-bis (butoxythiocarbonylthio) -
1,3-thiabicyclo (8,2,1) tridec-5ene B. 105.5 0.4 n-butanol 300 ml 3 2,6-bis (methoxythiocarbonylthio) -
9-thiabicyclo (3,3,1) nonane A. 105.5 0.5 Methanol 300 ml 4th 2,6-bis (benzyloxythiocarbonylthio) -
(3,3,1) nonane A. 105.5 0.5 Benzyl alcohol 400 ml 5 2,6-bis (ethoxythiocarbonylthio) -9-
thiabicyclo (3,3,1) nonane A. 211 0.5 Ethanol 300 ml 6th 2,6-bis (ethoxythiocarbonylthio) -9-
thiabicyclo (3,3,1) nonane A. 105.5 1.0 Ethanol 600 ml 7th 2,6-bis (isopropoxythiocarbonylthio) -
9-thiabicyclo (3,3,1) nonane A. 66.3 0.5 Isopropanol 450 ml 8th 2,9-bis (isopropoxythiocarbonylthio) -
1,3-thiabicyclo (8,2,1) -tridec-5-ene B ¹ 53.0 0.25 Isopropanol 200 ml 9 2,9-bis (2-ethylhexanoxythio-
carbonylthio) -1,3-thiabicyclo-
(8,3,1) tridec-5-en B ¹ 53.0 0.2 2-ethylhexanol 300 ml 10 2,9-bis (1-methylbutoxythiocarbonyl-
thio) -1,3-thiabicyclo (8,2,1) tridec-
5-en B ¹ 0.2 Pentan-2-ol 240 ml

to

K) U)

Table I (continued)

cn ο co CD CaJ CD \ O CO OO

at
game KOH weight
(G) CS, weight
(G) Reflux
Time temp.
(Hrs.) ( ⁰ C) 90 100 yield
g% 81.2 % S
found ber. % Cl 2 59.3 68.4 4th 5 3/4 67 74 160 70.4 30.7 32.5 0.52 3 72.2 83.6 5 74 124 87.4 44.9 45.2 0.74 4th 72.2 83.6 4th 74 221 82.3 28.5 31.7 0.3 5 72.2 83.6 4th 78 157 79.2 41.3 41.9 0.47 6th 144.4 167.2 4th 80 303 92.0 40.0 41.9 0.5 7th 72.2 84 3 80 188 L 81.2 34.0 39.0 0.5 8th 39.5 45.6 3 94,] 79.7 30.08 34.5 0.28 9 20, O ⁺ 38.0 3 96.4 86.1 24.97 26.5 0.29 10 32.9 38.0 89.5 27.2 30.8 0.75

+ NaOH used instead of KOH

to ι

cn σ co cn fs} U)

Table I (port setting)

cn ο CD OO to

CD CD GO 30th

at
game 2,9-bis (benzyloxythiocarbonylthio) -
1,3-thiabicyclo (8,2,1) tridec-5-ene ischei
oduct G Mole alcohol lot 11 2,6-bis (n-propoxythiocarbonylthio) -
9-thiabicyclo (3,3,1) nonane B ¹ 53.0 0.2 Benzyl alcohol 200 ml 12th 2,6-bis (1-methylpropoxythiocarbonyl-
thio) -9-thiabicyclo (3,3,1) nonane A ¹ 211 1.0 n-propanol 700 ml 13th 2,6-bis (1-methylbutoxythiocarbonyl-
thio) -9-thiabicyclo (3,3,1) nonane A ¹ 105.5 0.5 sec-butanol 400 ml 14th 2,6-bis (1-ethylpropoxythiocarbonyl-
thio) -9-thiabicyclo (3,3,1) nonane A ¹ 52.8 0.25 Pentan-2-ol 450 ml 15th 2,6-bis (2-ethylhexanoxythiocarbonyl-
thio) -9-thiabicyclo (3,3,1) nonane A ¹ 105.5 0.5 Pentan-2-ol 1100 ml 16 2,6-bis (tridecanoxythiocarbonylthio) -
9-thiabicyclo (3,3,1) nonane A ¹ 211 1.0 2-ethylhexanol 700 ml 17th 2,6-bis (allyloxythiocarbonylthio) -9-
thiabicyclo (3,3,1) nonane A ¹ 211 1.0 Tridecanol 1600 ml 18th 2,6-bis (crotyloxythiocarbonylthio) -
9-thiabicyclo (3,3,1) nonane A ¹ 211 1.0 Allyl alcohol 600 ml 19th 2,6-bis (cyclohexyloxythiocarbonyl
thio) -9-thiabicyclo (3,3,1) nonane A ¹ 52.75 0.25 Crotyl alcohol 200 ml 20th A ¹ 52.75 0.25 Cyclohexanol 350 ml

cn κ?

U)

Table I (continued)

cn o co

at
game KOH weight
(G) CS, weight
² (g) Time
(Hours Reflux
Textip.
.) ( ⁰ C) 80 yield
g% . 84.6 % S
found ber. % Cl 11 32.9 38.0 3 85 90.0 83.6 27.8 30.1 0.60 12th 144.4 167.2 3 70-80 342.7 92.2 38.5 39.0 0.56 13th 72.2 84.0 3 90 201.9 95.2 34.2 36.6 0.36 14th 49.5 57.0 3 1/2 80 111.0 78.8 32.4 34.4 0.33 15th 72.2 84.0 2 82-85 183.7 90.0 32.9 34.4 0.49 16 144.4 167.2 4th 90 495.3 91.0 28.1 29.1 0.46 17th 158 183 4th 80 628.2 89.3 23.15 23.2 0.14 18th 145 167 3 55-60 362.5 96.5 38.1 39.5 0.64 19th 39.5 45.6 3 80 104.7 71.8 36.2 36.87 0.26 20th 39.5 45.6 3 88.0 31.63 32.65 0.27

Example 21

Preparation of intermediate 2, e-dichloro-g-thiabicyclo (3,3,1) nonane sulfur dichloride (1030 g, -10 mol) and 1,5-cyclooctadiene (1080 g; 10 mol) were simultaneously in equal molar amounts to methylene dichloride ( 1250 ml), which was kept at 0 to -5 ° C over a period of 4 1/2 hours. The resulting mixture was allowed to warm to room temperature overnight, then heated to 45 ° C. for 2 hours, cooled to room temperature and cooled in order to obtain 1670.6 g (79.3%) of a solid product, which was filtered off and in vacuo. was dried in a drying cabinet at 50 ° C. Elemental analysis:% S 14.86 (calculated 15.1%)

% C1 31.7 (calculated 33.7)

Production of 2,6-bis (methoxy / jithoxythiocarbonylthio) -9-thiabicyclo (3,3,1) nonane

Potassium hydroxide (72.2 g; 1.1 mol) of 85% purity was added to a mixture of alcohols (ethanol 177 'g + methanol 123 g) and heated until it was dissolved. The resulting mixture was heated to about 40 ° C cooled and carbon disulfide (84 g; 1.1 mol) added, while the reaction temperature was kept ^{at about 40 0C.} A solution of the intermediate prepared above (105.5 g; 0.5 mol, dissolved in 400 ml of toluene) was then added over a period of 40 minutes. The tem-

- 16-

509836/0989

temperature was kept between 40 and 50 ° C. A yellow precipitate formed. The reaction mixture was heated under reflux (72 ° C) for 4 hours, then - after adding toluene to ensure phase separation - washed with water and the separated organic layer. The organic layer was filtered off over anhydrous magnesium sulfate dried overnight, again filtered off, at 100 ° C /

Stripped 20 torr and the residue again filtered through 106 g (57.6%) of the product as a viscous red liquid to obtain.

Elemental analysis: 44.7% S (calculated 43.5%)

0.65% Cl (calculated 0%)

Example 22

2,6-bls (methoxy / n-butoxythiocarbonylthio) -9-thiabicyclo- (3,3,1) nonane

The intermediate was prepared in the same manner as in Example 21 from 940 ml of methylene dichloride, 774 g (7.5 mol) Sulfur dichloride and 810 g (7.5 moles) 1,5-cyclooctadiene manufactured.

Elemental analysis: 16.4% S (calculated 15.1%)

33.5% Cl (calculated 33.7%).

The product was made in the same way as in Example

21 from 36.1 g of potassium hydroxide with 85% purity, one Mixture of 61.6 g of methanol and 142.5 g of n-butanol, 42 g

509836/09 89 -17-

(0.55 mole) carbon disulfide and 52.7 g (0.25 mole) Intermediate, which was dissolved in 200 ml of toluene, prepared. The yield was 59.7 g. Elemental analysis: 39.2% S (calculated 40.4%)

0.6% Cl (calculated 0%)

Example 23

The same product as in Example 22 was prepared in the same manner except that the Mixture of alcohols consisted of 31.4 g of methanol and 212 g of n-butanol. The yield was 80.1 g. Elemental analysis: 39.4% S (calculated 38.3%)

0.33% C1 (calculated 0%)

Example 24

2-All · yloxythiocarbonylthio-6-isopropyloxythiocarbonylthio-9-thiabicyclo (3,3,1) nonane

The product was prepared in the same manner as in Example 21 from potassium hydroxide (72.5 g, 1.1 mol, 85% purity), a mixture of allyl alcohol (145 g, 2.5 mol), isopropyl alcohol (150 g, 2, 5 moles), carbon disulfide (83.6 g, 1.1 mol) and 2,6-dichloro ⁱ -9-thiabicyclo (3,3, l) nonane (105.5 g, 0.5 mol) in 400 ml Toluene produced. The yield was 150 g (73.5%). Elemental analysis: 37.5% S (calculated 39.2%)

0.35% Cl (calculated 0.0%)

- 18 509836/0989

Example 25

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

(a) Potassium hydroxide (36.1 g; 0.55 mol; 85% purity) was dissolved in ethanol (150 ml) by heating at 50 ° C for 10 minutes. The solution was ^{cooled to 40 °} C. and carbon disulfide (41.8 g; 0.55 mol) was added over a period of 20 minutes and then toluene (50 ml) was added with stirring. A solution of 2,6-dichloro-9-thiabicyclo (3.3.1) nonane (105.5 g; 0.5 mol) in toluene (400 ml) was added over 40 minutes with cooling. The temperature was allowed to exotherm 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 filtered off. 2 phases were obtained. After drying over magnesium sulphate and filtering off, the solvent was stripped off and the product (a) was obtained.

(b) potassium hydroxide (36.1 g; 1.1 mol; 85% purity) was dissolved in methanol (150 ml) in a fresh glass container. Carbon disulfide (41.8 g; 0.55 mole) added with stirring over a period of half an hour. The product (a), dissolved in toluene (400 ml), was added over 3/4 hour and the mixture heated to 64 ° C for 4 hours. After cooling down

- 19 509836/0989

the product was washed with three portions of water and toluene was added as a separation aid. After this Drying over magnesium sulfate, filtering off and stripping off gave 150 g (81.5 g%) of the above product obtained as a viscous orange liquid. Elemental analysis: 35.6% S (calculated 43.5%)

0.75% Cl (calculated 0.0%)

Three other examples (Examples 26-28) were prepared in essentially the same manner as in Example 25 described carried out. Only the individual reactants and the elemental analyzes were given in each case .

Example 26

2,6-bis (methoxy / butoxythiocarbonylthio) -9-thiabicyclo- (3.3, l) nonane

(a) KOH (72.2 g; 1.1 mol; 85% purity), n-butanol (400 ml), CS ₂ (83.6 g; 1.1 mol), 2,6-dichloro-9 thiabicyclo (3.3, l) nonane (211 g, 1 mol) and toluene (800 ml);

(b) KOH (72.2 g; 1.1 mol, 85% purity), methanol (300 ml), CS ₂ (83.6 g; 1.1 mol) and toluene (600 ml).

The reaction product from (a) was added to (b).
The yield of the end product was 332.8 g (84%). Orange liquid.

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50 9836/0989

Elemental analysis: 31.7% S (calculated 40.4%)

0.55% C1 (calculated 0.0%)

Example 27

2,6-bis (ethoxy / butoxythiocarbonylthio) -9-thiabicyclo- (3,3,1) nonane

(a) KOH (18 g; 0.275 mol; 85% purity), n-butanol (100 ml), CS ₂ (21 g; 0.275 mol), 2,6-dichloro-9-thiabicyclo (3.3, l ) -nonane (52.8 g; 0.25 mol), toluene (200 ml).

(b) KOH (18 g; 0.275 mol; 85% purity), ethanol (100 ml), CS ₂ (21 g; 0.275 mol) and toluene (200 ml).

The reaction product from (a) was added to the reaction product from (b).

The yield of the end product was 72.6 g (71%). Elemental analysis: 31.4% S (calculated 39%)

0.5% Cl (calculated 0.0%)

Example 28

2-Allyloxythiocarbonylthio-6-isopropoxythiocarbonylthio-9-thiabicyclo (3,3,1) nonane

(a) KOH (32.9 g; 0.5 mol; 85% purity), isopropyl alcohol (200 ml), CS ₂ (38 gr 0.5 mol), 2,6-dichloro-9-thiabicyclo (3, 3, l) nonane (105.5 g; 0.5 mol), toluene (400ml)

(b) KOH (39.5 g; 0.6 mol; 85% purity), allyl alcohol

- 21 509836/0989

(150 ml), CS ₂ (45.6 g; 0.6 mol).

The reaction product from (a) was added to the reaction product (b).

The yield of the end product was 176.4 g (86.5%). Elemental analysis: 34.02% S (calculated 39.2%)

0.41% Cl (calculated 0.0%).

Example 29

2-dodecylthio-6-isopropoxythiocarbon ^ lthio-9-thiabicyclo (3,3,1) nonane

n-DodecyMercaptan (50.5 g; 0.25 mol) was added with stirring dissolved in toluene (200 ml) followed by sodium metal (5.8 g; 0.25 mol) over a period of 20 minutes added at 100 ° C. After heating at 110 ° C. for 2 hours, a white suspension was obtained which turned into a Solution of 2,6-dichloro-9-thiabicyclo- (3.3, l) nonane (211 g; 0.25 mol) in toluene (200 ml) over a period of 5 Minutes and then heated to 100 ° C. for 3 hours, cooled and filtered through a glass fiber filter became and a solution of potassium isopropylxanthate in Isopropyl alcohol was given.

The latter was prepared by adding potassium hydroxide (20 g; 0.3 mol; 85% purity) in isopropyl alcohol

material

was dissolved and carbon disulphides ^! 22.8 g; 0.3 mol) was added was while the temperature fell to 38 to 40 ° C

509836/0989

was holding. The mixture was heated to 80 ° C for 3 hours, cooled, washed with water and dried over magnesium sulfate and 101.4 g (85.2%) of the desired Product received.

Elemental analysis: 26.1% S (calculated 26.9%)

0.68% Cl (calculated 0.0%)

Examples 30 to 37

Further compounds of the invention were essentially in the same manner as described in Example 29 prepared. The individual reactants and elemental analyzes are summarized in Table II, in which, for the sake of simplicity, 2,6-dichloro-9-thiabicyclo- (3,3,1) nonane was abbreviated as 2,6-DTN.

- 23 -

509836/0983

Table II

example

product

Nucleophi-alkali

ler starting weight weight

fabric (g) (q)

Toluene (ml)

30 2-0 iisobutyl) dithiophosphate-6-diisobutylisopropoxythiocarbonylthio-9-thiabidithio-phoscyclo (3,3,1) nonane phosphoric acid

Ethyl, N
· * 25.3

100

CD 00 LO

31 2- (N, N-dibutyl-thiocarbamylthio) -6- N, N-dibutyl-

(isopropoxythiocarbonylthio) -9- thiocarbamate ++++ thiabicyclo (3,3,1) nonane

32 2- (butoxythiocarbonylthio) -6-

phenoxy-9-thiabicyclo (3,3,1) nonane

phenol

47

Na metal

11.5

1200

33 2- (Butoxythiocarbonylthio) -6- (o-t-Butylt-butyl-p-methylphenoxy) -9-thiap-cresol bicyclo (3,3,1) nonane

82

Na metal

11.5

800

. ι to

++++ Sodium N ^ -dibutyl-dithio-carbamate was prepared by adding NaOH (10 g; 0.25 mol) in a mixture of water (15 ml) and ethanol (40 ml) and di-n-butylamine (32.3 g; 0.25 mol) was dissolved. The mixture was cooled below 40 ° C and below that temperature held while carbon disulfide (13 g; 0.25 mole) was added. 2,6-DTN

in toluene was added. ^ _n

O OO CO

Table II (continued

cn ο CD co co CD

O UD 00 IO

(O

Ui

at
game 2,6-DTN
weight
(G) toluene
ml KOH
weight
(he) alcohol
Name amount
ml 150 CS ₂ -Ge-
weight
(Q) % S
found ber. ber.
(0.00) Other elements 30th 52.8 200 19.8 Iso-
propanol 11 22.8 32.1 31.0 0.23 element gef, ber. 31 52.8 19.8 Il 200 Il 28.8 33.4 0.26 P. 5.86 6. 32 105.5 400 33.0 n-butanol 2OO 38 23.4 25.1 0.39 N 3.27 2.92 33 105.5 400 33.0 n-butanol 38 21.4 21.2 0.22 - - * - -

I NJ

ro cn ο CG CD ro 00

Table II (continued)

cn o co

to co to

example

product

Nucleophi-alkali

ler initial weight name weight
substance (σ) (σ)

34 2- (Isopropoxythiocarbonylthio) -6- t-butyl- (ot-butyl-p-methylphenoxy) -9-p-cresol thiabicyclo (3,3,1) nonane Na- 23
metal

37 2- (hexanoxythiocarbonylthio) -6-isothioisothiocyanate-9-thiabicyclocyanate (3,3,1) nonane potassium salt

48.5

toluene

ml

1500

35 2- (butoxythiocarbonylthio) -6- (2,6-
di-t-butyl-p-methylphenoxy) -9-
thiabicyclo (3,3,1) nonane 2,6-di-t.-
butyl-p-
cresol 110 Na-
metal 11 , 5 800 36 2- (Octanoxythiocarbonylthio) - 6-
isothiocyanate-9-thiabicyclo-
(3,3,1) nonane Isothio
cyanate Potassium salt 48 , 5 1000 ⁺⁺

iooo

++ Methyl ethyl ketone, used as a solvent

cn ο co cn

Table II (porting)

cn CD CO oo GJ cn ^.

CD OO

I «ο

At- 2,6-DTN toluene KOH alcohol CS ₀ -% S% C1 other elements

game weight name amount _{weight f # ber> ber} . _{Element found ber} .

(g) ml (g) ml. j *%%

34 211 , 5 800 72.2 Iso-
propyl 400 83 , 6 21.1 21.86 0.38 - - - 35 105 , 5 400 36.1 n-Bu-
tanol 200 42 18.5 18.9 0.42 - - - 36 105 , 5 500 52.6 n-0c-
tanol 450 60 ,8th 28.5 31.8 0.40 N 2.18 3.4 37 105 500 52.6 n-hexa-
nol 400 60 ,8th 31.8 34.2 0.39 N 2.50 3.7

IO

- 2 / -

Example 38

2- (Octanoxythiocarbonylthio) -g-cyano-lS-thiabicyclo- (8,2,1) -tridec-5-en

(a) sodium cyanide (12.3 g; 0.25 mol), ethanol (3OO ml) and 2,9-dichloro-13-thiabicyclo (8.2,1) tridec-5-ene (66.3 g; 0.25 mol) were mixed and the exothermic reaction caused the temperature to rise to 35 ° C for one hour. Afterward was heated to 75 ° C for 3 hours. Then cooling water (600 ml) was added to precipitate a product, which was filtered off and dissolved in toluene.

(b) Potassium hydroxide (19.8 g; 0.3 mol; 85% purity) was dissolved in n-octanol (200 ml) by half a Was heated to 70 ° C. for an hour. After cooling to below 40 ° C was over a period of 20 minutes Carbon disulfide (22.8 g; 0.3 mol) was added and a yellow precipitate was obtained. The toluene solution of

(a) was added over a period of one hour and the mixture was heated to 90 ° C for 3 hours. To the solution was cooled 3 times with water (each

400 ml) and 400 ml of toluene as phase separation agent

help ^ admitted. The toluene solution was over magnesium sulfate dried and stripped with a rotary evaporator and then stripped in a high vacuum at 70 ° C / 0.1 torr to 120 ° C / 0.2 torr. The rest was one viscous brown liquid that appeared to be the desired product. - 28 -

509836/0989

Elemental analysis: 13.8% S (calculated 22.6%)

0.94% Cl (calculated 0.0%) 3.05% N (calculated 3.29%)

Example ° 39

2-ethylhexyl-xanthate of a polymer of 2,9-dichloro, 3-thiabicyclo (8.2, l) tridec-5-en

Cis, trans, trans-cyclododeca-l, 5,9-triene (324 g; 2 mol) and sulfur dichloride (206 g; 2 mol) were added simultaneously from two dropping funnels into stirred dichloromethane (1000 ml). The dichloromethane was maintained at a temperature of 0 to -5 ° C by an acetone / dry ice bath with a molar ratio of 2: 1. The mixture was allowed to warm to room temperature over the weekend. After refluxing (45 ° C) for 4 hours, it was allowed to cool in a refrigerator to allow it to crystallize. Since no crystals were formed, the solvent was removed with a rotary evaporator. Particularly boiling petroleum ether and 2 ^ - bicyclo (8.2, l) tridec-5-ene (DCTT) were dissolved with stirring at 62-68 ° C. A light brown solid polymer remained, which was also insoluble in toluene.
Elemental analysis: 12.7% S (calculated 12.07%)

23.8% Cl (calculated 26.8%) The values correspond to a polymer of the DCTT.

- 29 -

509836/0989

Potassium hydroxide (49.4 g; 0.75 moles; 85% purity) was Dissolved in 2-ethylhexanol (500 ml) by heating to 90 ° C for half an hour, cooling to below 40 ° C and Carbon disulfide (57 g; 0.75 moles) was added over a period of 25 minutes. Toluene (100 ml) added to maintain a liquid. DCTT polymer (66.3 g; 0.25 mol) in 2-ethylhexanol (500 ml) was added over a 45 minute period. The solution was heated to 80 - 85 ° C for 4 hours, cooled, diluted with toluene (600 ml), washed 4 times with water (400 ml each time), dried over magnesium sulfate and filtered. After removing the solvent on a rotary evaporator, the product was in a high vacuum stripped at a base temperature of 80 ° C / 0.1 Torr .

Elemental analysis: 15.8% S (calculated 26.5%)

1.06% C1 (calculated 0.0%).

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 (boiling point 62 ° -68 ° C.). A solid polymer remained which contained 12.06% S and 28% Cl.
A polar reaction was then carried out as in Example 39

- 30 -

509836/0989

described, carried out and there were 80 g of the product obtain.

Elemental analysis: 25.1% S (calculated 26.5%)

1.71% Cl (calculated O, O%)

Example 41

2,9-bis (crotyloxythiocarbonylthio) -13-thiabicvclo (8,2,1) -tridec-5-ene

Example 19 was repeated except that Intermediate B (66.3 g; 0.25 mol) was used in place of the Intermediate A was used. The product yield was 112 g (91.4%).

Elemental analysis: 30.5% S (calculated 32.7%)

1.27% C1 (calculated 0.0%)

Example 42

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

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

- 31 -

509836/0989

The intermediate product prepared in the previous section (114 g; 0.58 mol), dissolved in 200 ml of toluene, was added to 1.3 mol of potassium isopropylxanthate and the mixture was ^{heated to 80 °} C. for 5 hours. More toluene was then added and the resulting solution washed with water and dried over magnesium sulfate. The toluene was then stripped on a rotary evaporator and 146.4 g (64.1%) of a black liquid was obtained.
Elemental analysis: 38% S (calculated 40.6%)

2.34% Cl (calculated 0.0%)

Try A to R

Certain compounds described in the above examples were dissolved in lubricating oil (1% solutions) and examined in the extended so-called Petter-Wl test.

The experiments were carried out for 36 hours using a Petter Wl laboratory machine. The machine and the procedure corresponded to the standard regulation IP 176/69 with the exception that an oil sample was not taken after 16 hours. The test mixes contained an ashless dispersant, an antioxidant, a surfactant and a corrosion inhibitor.

The bearing weight loss was taken as the criterion,

- 32 -

509836/0989

which is of the same order of magnitude or less than the storage weight loss for zinc dialkyldithiophosphate was.

Examples 1 and 2 gave blackened bearings when however, if the mixtures were tested again with 0.01% benzotriazole, the bearings had a normal color.

The products of Examples 4 and 5 gave particularly low bearing weight losses and the bearings had good color in the absence of benzotriazole.

The product of Example 3 was only 0.25% soluble in mineral oil.

The results of these tests are given in Table III. From this it can be seen that the results are comparatively cheap compared to a mixture containing a zinc dialkyldithiophosphate, and compared to other ash-containing additives.

In addition, copper strip tests were carried out using the IP test method 154/69 carried out with the exception that the tests at 120 ° C using the test additive were carried out. The test additive was dissolved in 500 Solvent Neutral Mineral Oil in an amount sufficient to a product with a sulfur concentration

509836/0989 - 33 -

of 0.15% by weight. That way each became of the products of Examples 1, 2, 4, 5, 7 to 13, 16, 19, 25, 28 to 36 and 39 to 41 were examined. All led to la or ib results.

The new additives according to the invention also had useful loading properties.

- 34 -

509836/0989

Table III

Ver
search Mixture that
contains 1%
of example Frictional
weight
loss (mg) colour A. 1 22nd black B. 2 30th black C. 4th 8th straw-colored D. 5 7th Il E. 7th 17th Il P. 12th 8.1 brown to dark
stains G 13th 16 slightly straw-colored
dark, straw-colored
stains H 14th 14th straw-colored
dark, straw-colored
stains I. 15th 14th slightly straw-colored
peacock colors J 16 53.3 dark brown -
black lacquer K 17th 22nd brownish - peacocks
Colours L. 28 (1.5%) 19th brown with black
traces M. 32 17th straw-colored - peacocks
Colours

- 35-

509836/0989

Table III (continued)

Ver
search Mixture that
contains 1%
of example Frictional
weight
loss (mg) colour N 33 12th brown with black
traces O 34 18th straw-colored - peacock-
Colours P. 35 12th straw-colored paint
traces Q 36 8th straw-colored - peacock-
Colours R. 39 20th slightly straw-colored -
copper / peacock colored
stains

509836/0989

- 36 -

Claims (46)

Claims Connections of the formulas S S ARSC-OR ¹ or R ¹ O -C = S (I) (II) wherein in formula (I) R is the residue of an intramolecularly bridged hydrocarbon ring with sulfur 6 to 12 carbon atoms or wherein in formula (II) -J-R-J- is a polymer which consists of the remainder of several essentially It consists of intermolecular sulfur-bridged hydrocarbon rings, each of which consists of 6 to 12 Has carbon atoms, η is the degree of polymerization, each R radical is identical or different and an alkyl, alkenyl or aralkyl and A is nucleophilic. 2. Compounds according to claim 1, characterized in that that each R radical is an alkyl or alkenyl radical having 2 to 8 carbon atoms. 3. Compounds according to claim 1 or 2, characterized Γ 2 ~ l characterized that R or.4-R -4 are derived from 1,3,5-cycloheptatriene, cyclooctatetraene, 1,3-cyclooctadiene, 1,5-cyclooctadiene or a 3-alk- 509836/0 989 ~ ³⁷ ' Oxy derivative derived therefrom or from cis, trans, trans-l _/ 5 _> 9-cyclododecatriene. 4. Compounds according to claim 1 to 3, characterized in that the radical A has the formula S-C - OR in which R ^{± has} the meaning given in claim 1 and in which the two R radicals can be identical or different. 5. Compounds according to claim 4, characterized in that that one R group is ethyl or propyl and the other R group is methyl, ethyl or propyl. 6. Compounds according to Claims 1 to 3, characterized in that the remainder A has the formulas R ³ 3 3 S " -XH, -XR, -XC-R, -XCN \ or η "χ 3 XX ^N R -XP-OR ³ X OR ³ wherein X is oxygen or sulfur and R is an alkyl, aryl, alkaryl or aralkyl radical. - 38 509836/0989 7. Compounds according to claim 1 to 3, characterized in that the radical A -CN or -NCS is. 8th . 2,6-bis (butoxythiocarbonylthio) -9-thiabicyclo (3,3,1) -nonane. 9. 2,9-bis (butoxythiocarbonylthio) -1,3-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-thiabicyclo (3,3,1) nonane. 14. 2,9-bis (isopropoxythiocarbonylthio) -1,3-thiabicyclo (8.2.1) tridec-5-ene. 15. 2,9-bis (2-fithylhexanoxythiocarbonylthio) -1,3-thiabicyclo (3,3,1) tridec-5-en. -39-509836 / 0989 16. 2,9-bis (1-methylbutoxythiocarbonylthio) -1,3-thiabicyclo (8,2,1) tridec-5-en. 17. 2,9-bis (Benzyloxythiocarbonylthio) -1,3-thiabicyclo- (8,2,1) tridec-5-ene. 18. 2,6-bis (n-Propoxythiocarbonylthio) -9-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. - 40 - 509836/0989 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) dithiophosphate-6-isopropoxythiocarbonylthio-9-thiabicyclo (3,3,1) nonan. 32. 2- (N, N-dibutylthiocarbamylthio) -6- (isopropoxythiocarbonylthio-9-thiabicyclo) - (3,3,1) nonane. 33. 2- (Butoxythiocarbonylthio) -e-phenoxy ^ -thiabicyclo- (3,3,1) nonane. - 41 509836/0989 34. 2- (Butoxythiocarbonylthio) -6- (o-t-butyl-p-methylphenoxy) -9-thiabicyclo (3,3,1) nonane. 35. 2- (Isopropoxy-thiocarbonylthio) -6- (o-t -butyl-pmethylphenoxy-9-thiabicyclo) (3,3,1) nonane. 36. 2- (Butoxythiocarbonylthio) -6- (2,6-di-t-butyl-pmethylphenoxy) -9-thiabicyclo (3,3,1) nonane. 37. 2- (Octanoxythiocarbonylthio) -6-isothiocyanato-9-thiabicyclo (3,3,1) nonane. 38. 2- (hexanoxythiocarbonylthio) -6-isothiocyanate-9-thiabicyclo (3,3,1) nonane. 39. 2- (Octanoxythiocarbonylthio) -9 ~ cyano-13-thiabicyclo- (8,2,1) -tridec-5-en. 40. 2,9-bis (crotyloxythiocarbonylthio) -13-thiabicyclo- (8,2,1) tridec-5-en. 41. 2,6-bis (isopropoxythiocarbonylthio) -8-thiabicyclo- (3.2.1) oct-3-ene. 42. Process for the preparation of compounds, characterized in that an alkyl, Alkenyl or aralkyl xanthate or a metal salt thereof 509836/0989 in a molar ratio of 2: 1 with a sulfur-bridged dichloro compound of the formula Cl-R-Cl or with formation of compounds of the formulas R ¹ O -C = S FSC- OR ¹ J ₂ or —j- R ² -J-; ■ R ¹ O -C = S (III) (IV) 1 2
is reacted, wherein R, R, R and η are those in claim 1 have given meaning. 43. A process for the preparation of compounds, characterized in that an alkyl, Alkenyl or aralkyl xanthate or a metal salt thereof in a 1: 1 molar ratio with one with sulfur bridged dichloro compound of the formula Cl-R-Cl or Cl Γ * 2 "" i -f- ft -p with the formation of an intermediate product is set, which is then in a molar ratio of 1: 1 with a metal salt of a nucleophilic radical Formation of compounds of the formulas - 43 - 509836/0989 S * ARSC- OR ¹ or S (I) _χ R ^x 0 -C = S (ID 1 2 is reacted, in which A, R, R, R and η have the meaning given in claim 1. 44. Process for the preparation of compounds, characterized in that a metal salt of a nucleophilic radical in a molar ratio of 1: 1 with a sulfur-bridged dichloro compound of the formula Cl-R-Cl or Cl Cl is reacted to form an intermediate, which is then in a molar ratio of 1: 1 with an alkyl, alkenyl or aralkyl xanthate or a metal salt to form compounds of the formulas S S ARSC-OR ¹ or R ¹ O -C = S (D (II) 1 2 is reacted, wherein A, R, R, R and η are those in claim 1 have given meaning. - 44 509836/0989 45. Lubricant preparation, consisting of a lubricating oil and an additive, characterized in that that the additive is a compound of the formulas _ 4- "A ² V ARSC- OR ^X or, V ¹ (I) (H) R ¹ O -C = S where in formula (I) R is the residue of an intramolecularly sulfur-bridged hydrocarbon residue with 6-12 carbon atoms or in which in formula (II) - £ R J- is a polymer which consists of the remainder several, essentially intermolecular with sulfur bridged hydrocarbon rings, each of which has 6-12 C atoms, η is the degree of polymerization is, each R radical is identical or different and an alkyl, alkenyl or aralkyl radical and A is a nucleophilic residue. 46. lubricant preparation according to claim 45, characterized in that the Compound of formula (I) or (II) is a compound claimed in claims 2 to 41. 509836/0989