Patent Publication Number: US-8530686-B2

Title: Organic molybdenum compounds and lubricating compositions which contain said compounds

Description:
CROSS-REFERENCE TO RELATED APPLICATIONS 
     The present application is a continuation of U.S. Ser. No. 12/525,359, filed on Nov. 25, 2009, which claims priority from PCT/US2008/051258, filed Feb. 1, 2008, which claims priority from JP 2007-023479, filed Feb. 1, 2007, all of which are incorporated herein by reference. 
    
    
     TECHNICAL FIELD OF THE INVENTION 
     The invention relates to novel organic molybdenum compounds, the use thereof as friction-modifiers and lubricating compositions which contain said compounds. 
     BACKGROUND OF THE INVENTION 
     Friction-modifiers (friction-adjusting agents) are used for adjusting the friction characteristics of a lubricant to an appropriate level. Friction-modifiers which reduce friction are used in lubricating compositions such as gear oils and engine oils with a view to reducing fuel costs. Friction-modifiers which raise friction are used for maintaining a certain high friction level in the lubricating compositions which are used in the wet-type clutch part of an automatic gear box. Many types of such friction-modifiers have been proposed. 
     The organic molybdenum compounds are the most typical of these friction-modifiers and, as shown in “Shinban Sekiyu Seihin Tenkasai” (New Edition, Additives for Petroleum Products), by Toshio SAKURAI, Saiwai Shobo Co., published 25 Jul. 1986, these organic molybdenum compounds are compounds which have two molybdenum atoms in one molecule as shown in formulae (2) and (3) below. 
                         
(Those compounds for which in this formulae x=0 and y=4, and for which x+y=4, and for which x≧2 are insoluble in oil and the others are oil-soluble.)
 
     Furthermore, compounds in which the element molybdenum is included twice in one molecule have been disclosed in Japanese Patent No. 3495764, Japanese Examined Patent Publication 45-24562, Japanese Unexamined Patent Application Laid Open 52-19629, Japanese Unexamined Patent Application Laid Open 52-106824, and Japanese Unexamined Patent Application Laid Open 48-56202. 
     A problem with catalyst poisoning in the apparatus which is used for cleaning-up the exhaust gas arises when compounds which contain phosphorus in the molecule as shown in the aforementioned general formula (2) are added to engine oils and there is a demand for compounds which are phosphorus-free. 
     SUMMARY OF THE INVENTION 
     An object of the present invention is to provide novel compounds which are useful as lubricating additives and the like which do not contain phosphorus, which reduce the friction coefficient and control the friction of a wet-type clutch, for example, optimally, and friction modifiers comprising said compounds. 
     A further object of the invention is to provide lubricating compositions which contain these compounds. 
    
    
     
       BRIEF EXPLANATION OF THE DRAWINGS 
         FIG. 1  is a graph showing how the friction coefficient changed with the passage of time with the lubricating oils of Example 5 and Comparative Example 1. 
         FIG. 2  is an outline drawing of the cylinder-on-disc reciprocating movement tester. 
     
    
    
     DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS 
     To achieve these objects, the present invention provides dicyclopentadienyl molybdenum crosslinked complexes having general formula (1) below. 
     
       
         
         
             
             
         
       
     
     In this formula X is the element oxygen or the element sulphur, Y is the element oxygen or Y is absent, and R 1  to R 10  are groups selected individually from the group comprising hydrogen, a methyl group and an ethyl group. 
     According to a preferred embodiment the dicyclopentadienyl molybdenum crosslinked complexes of general formula (1) can be represented by general formula (2) which is indicated below. 
                         
In this formula R 1  to R 10  are groups selected individually from the group comprising hydrogen, a methyl group and an ethyl group.
 
     According to a preferred embodiment the dicyclopentadienyl molybdenum crosslinked complexes of general formula (1) can be represented by general formula (3) which is indicated below. 
                         
In this formula R 1  to R 10  are groups selected individually from the group comprising hydrogen, a methyl group and an ethyl group.
 
     According to a preferred embodiment the dicyclopentadienyl molybdenum crosslinked complexes of general formula (1) can be represented by general formula (4) which is indicated below. 
     In this 
                         
formula R 1  to R 10  are groups selected individually from the group comprising hydrogen, a methyl group and an ethyl group.
 
     According to a preferred embodiment the dicyclopentadienyl molybdenum crosslinked complexes of general formula (1) can be represented by general formula (5) which is indicated below. 
                         
In this formula R 1  to R 10  are groups selected individually from the group comprising hydrogen, a methyl group and an ethyl group.
 
     Further the present invention provides the use of the dicyclopentadienyl molybdenum crosslinked complexes as friction-modifiers. 
     Also the present invention provides lubricating compositions which contain the compounds. 
     The compounds of this invention can be produced, for example, using the method indicated below. 
     First Process 
     Synthesis of the Synthesis Intermediate Raw Material Dicyclopentadienyl Molybdenum Hexa-Carbonyl Complex 
                         
Second Process
 
     Synthesis of the Dicyclopentadienyl Molybdenum Crosslinked Complex 
     The di(cyclopentadienyl) μ-thioxomolybdenum complex of general formula (2), the di(cyclopentadienyl) μ-thioxodioxomolybdenum complex of general formula (3), the di(cyclopentadienyl) μ-oxomolybdenum complex of general formula (4) and the di(cyclopentadienyl) μ-oxodioxomolybdenum complex of general formula (5) are produced simultaneously in accordance with the reaction equation indicated below. 
     
       
         
         
             
             
         
       
       
         
         
             
             
         
       
     
     Hydrogen, the methyl group and the ethyl group can be cited for the aforementioned R 1  to R 10 , and the compounds with combinations such as those shown in Tables 1 to 18 below can be cited. 
     
       
         
           
               
               
               
               
               
               
               
               
               
             
               
                 TABLE 1 
               
               
                   
               
               
                 Compound 
                 1  
                 2  
                 3  
                 4  
                 5 
                 6 
                 7 
                 8 
               
               
                   
               
             
            
               
                 X 
                 S 
                 S 
                 O 
                 O 
                 S 
                 S 
                 O 
                 O 
               
               
                 Y 
                 O 
                 — 
                 O 
                 — 
                 O 
                 — 
                 O 
                 — 
               
               
                 R 1   
                 H 
                 H 
                 H 
                 H 
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
               
               
                 R 2   
                 H 
                 H 
                 H 
                 H 
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
               
               
                 R 3   
                 H 
                 H 
                 H 
                 H 
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
               
               
                 R 4   
                 H 
                 H 
                 H 
                 H 
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
               
               
                 R 5   
                 H 
                 H 
                 H 
                 H 
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
               
               
                 R 6   
                 H 
                 H 
                 H 
                 H 
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
               
               
                 R 7   
                 H 
                 H 
                 H 
                 H 
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
               
               
                 R 8   
                 H 
                 H 
                 H 
                 H 
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
               
               
                 R 9   
                 H 
                 H 
                 H 
                 H 
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
               
               
                 R 10   
                 H 
                 H 
                 H 
                 H 
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
               
               
                   
               
            
           
         
       
     
     
       
         
           
               
               
               
               
               
               
               
               
               
             
               
                 TABLE 2 
               
               
                   
               
               
                 Compound 
                 9 
                 10 
                 11 
                 12 
                 13 
                 14 
                 15 
                 16 
               
               
                   
               
             
            
               
                 X 
                 S 
                 S 
                 O 
                 O 
                 S 
                 S 
                 O 
                 O 
               
               
                 Y 
                 O 
                 — 
                 O 
                 — 
                 O 
                 — 
                 O 
                 — 
               
               
                 R 1   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 H 
                 H 
                 H 
                 H 
               
               
                 R 2   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 H 
                 H 
                 H 
                 H 
               
               
                 R 3   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 H 
                 H 
                 H 
                 H 
               
               
                 R 4   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 H 
                 H 
                 H 
                 H 
               
               
                 R 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 H 
                 H 
                 H 
                 H 
               
               
                 R 6   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
               
               
                 R 7   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
               
               
                 R 8   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
               
               
                 R 9   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
               
               
                 R 10   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
               
               
                   
               
            
           
         
       
     
     
       
         
           
               
               
               
               
               
               
               
               
               
             
               
                 TABLE 3 
               
               
                   
               
               
                 Compound 
                 17 
                 18 
                 19 
                 20 
                 21 
                 22 
                 23 
                 24 
               
               
                   
               
             
            
               
                 X 
                 S 
                 S 
                 O 
                 O 
                 S 
                 S 
                 O 
                 O 
               
               
                 Y 
                 O 
                 — 
                 O 
                 — 
                 O 
                 — 
                 O 
                 — 
               
               
                 R 1   
                 H 
                 H 
                 H 
                 H 
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
               
               
                 R 2   
                 H 
                 H 
                 H 
                 H 
                 H 
                 H 
                 H 
                 H 
               
               
                 R 3   
                 H 
                 H 
                 H 
                 H 
                 H 
                 H 
                 H 
                 H 
               
               
                 R 4   
                 H 
                 H 
                 H 
                 H 
                 H 
                 H 
                 H 
                 H 
               
               
                 R 5   
                 H 
                 H 
                 H 
                 H 
                 H 
                 H 
                 H 
                 H 
               
               
                 R 6   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
               
               
                 R 7   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 H 
                 H 
                 H 
                 H 
               
               
                 R 8   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 H 
                 H 
                 H 
                 H 
               
               
                 R 9   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 H 
                 H 
                 H 
                 H 
               
               
                 R 10   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 H 
                 H 
                 H 
                 H 
               
               
                   
               
            
           
         
       
     
     
       
         
           
               
               
               
               
               
               
               
               
               
             
               
                 TABLE 4 
               
               
                   
               
               
                 Compound 
                 25 
                 26 
                 27 
                 28 
                 29 
                 30 
                 31 
                 32 
               
               
                   
               
             
            
               
                 X 
                 S 
                 S 
                 O 
                 O 
                 S 
                 S 
                 O 
                 O 
               
               
                 Y 
                 O 
                 — 
                 O 
                 — 
                 O 
                 — 
                 O 
                 — 
               
               
                 R 1   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
               
               
                 R 2   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 H 
                 H 
                 H 
                 H 
               
               
                 R 3   
                 H 
                 H 
                 H 
                 H 
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
               
               
                 R 4   
                 H 
                 H 
                 H 
                 H 
                 H 
                 H 
                 H 
                 H 
               
               
                 R 5   
                 H 
                 H 
                 H 
                 H 
                 H 
                 H 
                 H 
                 H 
               
               
                 R 6   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
               
               
                 R 7   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 H 
                 H 
                 H 
                 H 
               
               
                 R 8   
                 H 
                 H 
                 H 
                 H 
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
               
               
                 R 9   
                 H 
                 H 
                 H 
                 H 
                 H 
                 H 
                 H 
                 H 
               
               
                 R 10   
                 H 
                 H 
                 H 
                 H 
                 H 
                 H 
                 H 
                 H 
               
               
                   
               
            
           
         
       
     
     
       
         
           
               
               
               
               
               
               
               
               
               
             
               
                 TABLE 5 
               
               
                   
               
               
                 Compound 
                 33 
                 34 
                 35 
                 36 
                 37 
                 38 
                 39 
                 40 
               
               
                   
               
             
            
               
                 X 
                 S 
                 S 
                 O 
                 O 
                 S 
                 S 
                 O 
                 O 
               
               
                 Y 
                 O 
                 — 
                 O 
                 — 
                 O 
                 — 
                 O 
                 — 
               
               
                 R 1   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
               
               
                 R 2   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
               
               
                 R 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 H 
                 H 
                 H 
                 H 
               
               
                 R 4   
                 H 
                 H 
                 H 
                 H 
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
               
               
                 R 5   
                 H 
                 H 
                 H 
                 H 
                 H 
                 H 
                 H 
                 H 
               
               
                 R 6   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
               
               
                 R 7   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
               
               
                 R 8   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 H 
                 H 
                 H 
                 H 
               
               
                 R 9   
                 H 
                 H 
                 H 
                 H 
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
               
               
                 R 10   
                 H 
                 H 
                 H 
                 H 
                 H 
                 H 
                 H 
                 H 
               
               
                   
               
            
           
         
       
     
     
       
         
           
               
               
               
               
               
               
               
               
               
             
               
                 TABLE 6 
               
               
                   
               
               
                 Compound 
                 41 
                 42 
                 43 
                 44 
                 45 
                 46 
                 47 
                 48 
               
               
                   
               
             
            
               
                 X 
                 S 
                 S 
                 O 
                 O 
                 S 
                 S 
                 O 
                 O 
               
               
                 Y 
                 O 
                 — 
                 O 
                 — 
                 O 
                 — 
                 O 
                 — 
               
               
                 R 1   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
               
               
                 R 2   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 H 
                 H 
                 H 
                 H 
               
               
                 R 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 H 
                 H 
                 H 
                 H 
               
               
                 R 4   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 H 
                 H 
                 H 
                 H 
               
               
                 R 5   
                 H 
                 H 
                 H 
                 H 
                 H 
                 H 
                 H 
                 H 
               
               
                 R 6   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
               
               
                 R 7   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 H 
                 H 
                 H 
                 H 
               
               
                 R 8   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 H 
                 H 
                 H 
                 H 
               
               
                 R 9   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 H 
                 H 
                 H 
                 H 
               
               
                 R 10   
                 H 
                 H 
                 H 
                 H 
                 H 
                 H 
                 H 
                 H 
               
               
                   
               
            
           
         
       
     
     
       
         
           
               
               
               
               
               
               
               
               
               
             
               
                 TABLE 7 
               
               
                   
               
               
                 Compound 
                 49 
                 50 
                 51 
                 52 
                 53 
                 54 
                 55 
                 56 
               
               
                   
               
             
            
               
                 X 
                 S 
                 S 
                 O 
                 O 
                 S 
                 S 
                 O 
                 O 
               
               
                 Y 
                 O 
                 — 
                 O 
                 — 
                 O 
                 — 
                 O 
                 — 
               
               
                 R 1   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
               
               
                 R 2   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 H 
                 H 
                 H 
                 H 
               
               
                 R 3   
                 H 
                 H 
                 H 
                 H 
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
               
               
                 R 4   
                 H 
                 H 
                 H 
                 H 
                 H 
                 H 
                 H 
                 H 
               
               
                 R 5   
                 H 
                 H 
                 H 
                 H 
                 H 
                 H 
                 H 
                 H 
               
               
                 R 6   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
               
               
                 R 7   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 H 
                 H 
                 H 
                 H 
               
               
                 R 8   
                 H 
                 H 
                 H 
                 H 
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
               
               
                 R 9   
                 H 
                 H 
                 H 
                 H 
                 H 
                 H 
                 H 
                 H 
               
               
                 R 10   
                 H 
                 H 
                 H 
                 H 
                 H 
                 H 
                 H 
                 H 
               
               
                   
               
            
           
         
       
     
     
       
         
           
               
               
               
               
               
               
               
               
               
             
               
                 TABLE 8 
               
               
                   
               
               
                 Compound 
                 57 
                 58 
                 59 
                 60 
                 61 
                 62 
                 63 
                 64 
               
               
                   
               
             
            
               
                 X 
                 S 
                 S 
                 O 
                 O 
                 S 
                 S 
                 O 
                 O 
               
               
                 Y 
                 O 
                 — 
                 O 
                 — 
                 O 
                 — 
                 O 
                 — 
               
               
                 R 1   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
               
               
                 R 2   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
               
               
                 R 3   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 H 
                 H 
                 H 
                 H 
               
               
                 R 4   
                 H 
                 H 
                 H 
                 H 
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
               
               
                 R 5   
                 H 
                 H 
                 H 
                 H 
                 H 
                 H 
                 H 
                 H 
               
               
                 R 6   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
               
               
                 R 7   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
               
               
                 R 8   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 H 
                 H 
                 H 
                 H 
               
               
                 R 9   
                 H 
                 H 
                 H 
                 H 
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
               
               
                 R 10   
                 H 
                 H 
                 H 
                 H 
                 H 
                 H 
                 H 
                 H 
               
               
                   
               
            
           
         
       
     
     
       
         
           
               
               
               
               
               
               
               
               
               
             
               
                 TABLE 9 
               
               
                   
               
               
                 Compound 
                 65 
                 66 
                 67 
                 68 
                 69 
                 70 
                 71 
                 72 
               
               
                   
               
             
            
               
                 X 
                 S 
                 S 
                 O 
                 O 
                 S 
                 S 
                 O 
                 O 
               
               
                 Y 
                 O 
                 — 
                 O 
                 — 
                 O 
                 — 
                 O 
                 — 
               
               
                 R 1   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
               
               
                 R 2   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
               
               
                 R 3   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
               
               
                 R 4   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
               
               
                 R 5   
                 H 
                 H 
                 H 
                 H 
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
               
               
                 R 6   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
               
               
                 R 7   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
               
               
                 R 8   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
               
               
                 R 9   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
               
               
                 R 10   
                 H 
                 H 
                 H 
                 H 
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
               
               
                   
               
            
           
         
       
     
     
       
         
           
               
               
               
               
               
               
               
               
               
             
               
                 TABLE 10 
               
               
                   
               
               
                 Compound 
                 73 
                 74 
                 75 
                 76 
                 77 
                 78 
                 79 
                 80 
               
               
                   
               
             
            
               
                 X 
                 S 
                 S 
                 O 
                 O 
                 S 
                 S 
                 O 
                 O 
               
               
                 Y 
                 O 
                 — 
                 O 
                 — 
                 O 
                 — 
                 O 
                 — 
               
               
                 R 1   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
               
               
                 R 2   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
               
               
                 R 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
               
               
                 R 4   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
               
               
                 R 5   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
               
               
                 R 6   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
               
               
                 R 7   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
               
               
                 R 8   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
               
               
                 R 9   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
               
               
                 R 10   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
               
               
                   
               
            
           
         
       
     
     
       
         
           
               
               
               
               
               
               
               
               
               
             
               
                 TABLE 11 
               
               
                   
               
               
                 Compound 
                 81 
                 82 
                 83 
                 84 
                 85 
                 86 
                 87 
                 88 
               
               
                   
               
             
            
               
                 X 
                 S 
                 S 
                 O 
                 O 
                 S 
                 S 
                 O 
                 O 
               
               
                 Y 
                 O 
                 — 
                 O 
                 — 
                 O 
                 — 
                 O 
                 — 
               
               
                 R 1   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
               
               
                 R 2   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
               
               
                 R 3   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
               
               
                 R 4   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
               
               
                 R 5   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
               
               
                 R 6   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
               
               
                 R 7   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
               
               
                 R 8   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
               
               
                 R 9   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
               
               
                 R 10   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
               
               
                   
               
            
           
         
       
     
     
       
         
           
               
               
               
               
               
               
               
               
               
             
               
                 TABLE 12 
               
               
                   
               
               
                 Compound 
                 89 
                 90 
                 91 
                 92 
                 93 
                 94 
                 95 
                 96 
               
               
                   
               
             
            
               
                 X 
                 S 
                 S 
                 O 
                 O 
                 S 
                 S 
                 O 
                 O 
               
               
                 Y 
                 O 
                 — 
                 O 
                 — 
                 O 
                 — 
                 O 
                 — 
               
               
                 R 1   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
               
               
                 R 2   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
               
               
                 R 3   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 H 
                 H 
                 H 
                 H 
               
               
                 R 4   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 H 
                 H 
                 H 
                 H 
               
               
                 R 5   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 H 
                 H 
                 H 
                 H 
               
               
                 R 6   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
               
               
                 R 7   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
               
               
                 R 8   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 H 
                 H 
                 H 
                 H 
               
               
                 R 9   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 H 
                 H 
                 H 
                 H 
               
               
                 R 10   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 H 
                 H 
                 H 
                 H 
               
               
                   
               
            
           
         
       
     
     
       
         
           
               
               
               
               
               
               
               
               
               
             
               
                 TABLE 13 
               
               
                   
               
               
                 Compound 
                 97 
                 98 
                 99 
                 100 
                 101 
                 102 
                 103 
                 104 
               
               
                   
               
             
            
               
                 X 
                 S 
                 S 
                 O 
                 O 
                 S 
                 S 
                 O 
                 O 
               
               
                 Y 
                 O 
                 — 
                 O 
                 — 
                 O 
                 — 
                 O 
                 — 
               
               
                 R 1   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
               
               
                 R 2   
                 H 
                 H 
                 H 
                 H 
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
               
               
                 R 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
               
               
                 R 4   
                 H 
                 H 
                 H 
                 H 
                 H 
                 H 
                 H 
                 H 
               
               
                 R 5   
                 H 
                 H 
                 H 
                 H 
                 H 
                 H 
                 H 
                 H 
               
               
                 R 6   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
               
               
                 R 7   
                 H 
                 H 
                 H 
                 H 
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
               
               
                 R 8   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
               
               
                 R 9   
                 H 
                 H 
                 H 
                 H 
                 H 
                 H 
                 H 
                 H 
               
               
                 R 10   
                 H 
                 H 
                 H 
                 H 
                 H 
                 H 
                 H 
                 H 
               
               
                   
               
            
           
         
       
     
     
       
         
           
               
               
               
               
               
               
               
               
               
             
               
                 TABLE 14 
               
               
                   
               
               
                 Compound 
                 105 
                 106 
                 107 
                 108 
                 109 
                 110 
                 111 
                 112 
               
               
                   
               
             
            
               
                 X 
                 S 
                 S 
                 O 
                 O 
                 S 
                 S 
                 O 
                 O 
               
               
                 Y 
                 O 
                 — 
                 O 
                 — 
                 O 
                 — 
                 O 
                 — 
               
               
                 R 1   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
               
               
                 R 2   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
               
               
                 R 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
               
               
                 R 4   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 H 
                 H 
                 H 
                 H 
               
               
                 R 5   
                 H 
                 H 
                 H 
                 H 
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
               
               
                 R 6   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
               
               
                 R 7   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
               
               
                 R 8   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
               
               
                 R 9   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 H 
                 H 
                 H 
                 H 
               
               
                 R 10   
                 H 
                 H 
                 H 
                 H 
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
               
               
                   
               
            
           
         
       
     
     
       
         
           
               
               
               
               
               
               
               
               
               
             
               
                 TABLE 15 
               
               
                   
               
               
                 Compound 
                 113 
                 114 
                 115 
                 116 
                 117 
                 118 
                 119 
                 120 
               
               
                   
               
             
            
               
                 X 
                 S 
                 S 
                 O 
                 O 
                 S 
                 S 
                 O 
                 O 
               
               
                 Y 
                 O 
                 — 
                 O 
                 — 
                 O 
                 — 
                 O 
                 — 
               
               
                 R 1   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
               
               
                 R 2   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
               
               
                 R 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
               
               
                 R 4   
                 H 
                 H 
                 H 
                 H 
                 H 
                 H 
                 H 
                 H 
               
               
                 R 5   
                 H 
                 H 
                 H 
                 H 
                 H 
                 H 
                 H 
                 H 
               
               
                 R 6   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
               
               
                 R 7   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
               
               
                 R 8   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
               
               
                 R 9   
                 H 
                 H 
                 H 
                 H 
                 H 
                 H 
                 H 
                 H 
               
               
                 R 10   
                 H 
                 H 
                 H 
                 H 
                 H 
                 H 
                 H 
                 H 
               
               
                   
               
            
           
         
       
     
     
       
         
           
               
               
               
               
               
               
               
               
               
             
               
                 TABLE 16 
               
               
                   
               
               
                 Compound 
                 121 
                 122 
                 123 
                 124 
                 125 
                 126 
                 127 
                 128 
               
               
                   
               
             
            
               
                 X 
                 S 
                 S 
                 O 
                 O 
                 S 
                 S 
                 O 
                 O 
               
               
                 Y 
                 O 
                 — 
                 O 
                 — 
                 O 
                 — 
                 O 
                 — 
               
               
                 R 1   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
               
               
                 R 2   
                 H 
                 H 
                 H 
                 H 
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
               
               
                 R 3   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
               
               
                 R 4   
                 H 
                 H 
                 H 
                 H 
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
               
               
                 R 5   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 H 
                 H 
                 H 
                 H 
               
               
                 R 6   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
               
               
                 R 7   
                 H 
                 H 
                 H 
                 H 
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
               
               
                 R 8   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
               
               
                 R 9   
                 H 
                 H 
                 H 
                 H 
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
               
               
                 R 10   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 H 
                 H 
                 H 
                 H 
               
               
                   
               
            
           
         
       
     
     
       
         
           
               
               
               
               
               
               
               
               
               
             
               
                 TABLE 17 
               
               
                   
               
               
                 Compound 
                 129 
                 130 
                 131 
                 132 
                 133 
                 134 
                 135 
                 136 
               
               
                   
               
             
            
               
                 X 
                 S 
                 S 
                 O 
                 O 
                 S 
                 S 
                 O 
                 O 
               
               
                 Y 
                 O 
                 — 
                 O 
                 — 
                 O 
                 — 
                 O 
                 — 
               
               
                 R 1   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
               
               
                 R 2   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 H 
                 H 
                 H 
                 H 
               
               
                 R 3   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
               
               
                 R 4   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
               
               
                 R 5   
                 H 
                 H 
                 H 
                 H 
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
               
               
                 R 6   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
               
               
                 R 7   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 H 
                 H 
                 H 
                 H 
               
               
                 R 8   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
               
               
                 R 9   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
               
               
                 R 10   
                 H 
                 H 
                 H 
                 H 
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
               
               
                   
               
            
           
         
       
     
     
       
         
           
               
               
               
               
               
               
               
               
               
             
               
                 TABLE 18 
               
               
                   
               
               
                 Compound 
                 137 
                 138 
                 139 
                 140 
                 141 
                 142 
                 143 
                 144 
               
               
                   
               
             
            
               
                 X 
                 S 
                 S 
                 O 
                 O 
                 S 
                 S 
                 O 
                 O 
               
               
                 Y 
                 O 
                 — 
                 O 
                 — 
                 O 
                 — 
                 O 
                 — 
               
               
                 R 1   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
               
               
                 R 2   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
               
               
                 R 3   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
               
               
                 R 4   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
               
               
                 R 5   
                 H 
                 H 
                 H 
                 H 
                 H 
                 H 
                 H 
                 H 
               
               
                 R 6   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
               
               
                 R 7   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
               
               
                 R 8   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
               
               
                 R 9   
                 CH 3   
                 CH 3   
                 CH 3   
                 CH 3   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
                 C 2 H 5   
               
               
                 R 10   
                 H 
                 H 
                 H 
                 H 
                 H 
                 H 
                 H 
                 H 
               
               
                   
               
            
           
         
       
     
     Lubricating oils and greases, for example, can be cited as lubricating compositions of this invention. The amount of a compound of this invention in a lubricating composition is the same as with the conventional friction-modifiers, for example, being compounded in a proportion with respect to the composition generally of some 0.1 to 10 wt %. 
     There are no particular limitations regarding the base oil or grease used in lubricating composition according to the present invention, and various conventional greases, mineral oils and synthetic oils may be conveniently used. For the purpose of this description, the term “base oil” is meant to also include a grease base stock. 
     The base oil used in the present invention may conveniently comprise mixtures of one or more mineral oils and/or one or more synthetic oils. 
     Mineral oils include liquid petroleum oils and solvent-treated or acid-treated mineral lubricating oil of the paraffinic, naphthenic, or mixed paraffinic/naphthenic type which may be further refined by hydrofinishing processes and/or dewaxing. 
     Suitable base oils for use in the lubricating oil composition of the present invention are Group I, Group II or Group III base oils, polyalphaolefins, Fischer-Tropsch derived base oils and mixtures thereof. 
     By “Group I” base oil, “Group II” base oil and “Group III” base oil in the present invention are meant lubricating oil base oils according to the definitions of American Petroleum Institute (API) categories I, II and III. Such API categories are defined in API Publication 1509, 15th Edition, Appendix E, April 2002. 
     Suitable Fischer-Tropsch derived base oils that may be conveniently used as the base oil in the lubricating oil composition of the present invention are those as for example disclosed in EP 0 776 959, EP 0 668 342, WO 97/21788, WO 00/15736, WO 00/14188, WO 00/14187, WO 00/14183, WO 00/14179, WO 00/08115, WO 99/41332, EP 1 029 029, WO 01/18156 and WO 01/57166. 
     Synthetic oils include hydrocarbon oils such as olefin oligomers (PAOs), dibasic acid esters, polyol esters, and dewaxed waxy raffinate. Synthetic hydrocarbon base oils sold by the Shell Group under the designation “XHVI” (trade mark) may be conveniently used. 
     Effects of the Invention 
     (1) Novel phosphorus-free Mo-based friction-modifiers have been obtained. 
     (2) The compounds of this invention exhibit a low friction coefficient and they can be used in particular as friction modifiers for various types of energy-saving engine lubricating oils. 
     (3) The compounds of this invention are especially suitable for use as friction-modifiers for fuel-saving engine oils as they are phosphorus-free. 
     (4) There is no damage to the catalysts (removal of NOx) which are housed in automobile exhaust gas cleaning apparatus. 
     EXAMPLES 
     The invention is described below by means of Examples and Comparative Examples but the invention is not limited in any way by these examples. 
     Example 1 
     The synthesis of Compound 6 in the aforementioned Table 1, the case where X is S, there is no Y and R 1  to R 10  are CH 3 . 
     (i) First Process 
     
       
         
         
             
             
         
       
     
     Tetrahydrofuran (THF, 45 ml) was added to 3.75 g (18.8 mmol) of pentamethylcyclopentadiene and, after being cooled to −78° C., 12.5 ml (18.8 mmol) of Bu-Li were added dropwise and lithium pentamethylcyclopentadienyl was co-ordinated. Then 5 g (18.8 mmol) of molybdenum hexa-carbonyl were added to this material and heated under reflux for 48 hours and, after the reaction had been completed, the mother liquor was cooled to 0° C. Separately, 3.2 g (18.8 mmol) of iron(II) sulphate was added to a solution comprising a mixture of 100 ml of pure water and 20 ml of acetic acid and the solution so obtained was added dropwise to the mother liquor. The red coloured solution obtained was subjected to suction filtration, washed and dried and the di(pentamethylcyclopentadienyl)molybdenum hexa-carbonyl complex was obtained by recrystallization. Yield 24% 
     (ii) Second Process 
     
       
         
         
             
             
         
       
     
     The di(pentamethylcyclopentadienyl)molybdenum hexa-carbonyl complex (0.5 g, 0.79 mmol) and 0.69 g (5.84 mmol) of 3-sulphorane were dissolved in 100 ml of toluene and heated under reflux at 120° C. for 3 hours. After the reaction had been completed the solvent was removed and the reaction product was subjected to column chromatography and a red coloured complex was isolated. Yield 3% 
     Example 2 
     The synthesis of Compound 5 in the aforementioned Table 1, the case where X is S, Y is O and R 1  to R 10  are CH 3 . 
     
       
         
         
             
             
         
       
     
     The aforementioned di(heptamethylcyclopentadienyl)molybdenum hexa-carbonyl complex (0.5 g, 0.79 mmol) and 0.69 g (5.84 mmol) of 3-sulphorane were dissolved in 100 ml of toluene and heated under reflux at 120° C. for 3 hours. After the reaction had been completed the solvent was removed and the reaction product was subjected to column chromatography and an orange coloured complex was isolated. Yield 4% 
     Example 3 
     The synthesis of Compound 3 in the aforementioned Table 1, the case where X and Y are O and R 1  to R 10  are H. 
     (i) First Process 
     
       
         
         
             
             
         
       
     
     Tetrahydrofuran (THF, 45 ml) was added to 18.8 mmol of cyclopentadiene and, after being cooled to −78° C., 12.5 ml (18.8 mmol) of Bu-Li were added dropwise and the lithium pentamethylcyclopentadienyl was co-ordinated. Then 5 g (18.8 mmol) of molybdenum hexa-carbonyl were added to this material and heated under reflux for 48 hours and, after the reaction had been completed, the mother liquor was cooled to 0° C. Separately, 3.2 g (18.8 mmol) of iron(II) sulphate was added to a solution comprising a mixture of 100 ml of pure water and 20 ml of acetic acid and the solution so obtained was added dropwise to the mother liquor. The red coloured solution obtained was subjected to suction filtration, washed and dried and the di(cyclo-pentadienyl)molybdenum hexa-carbonyl complex was obtained by recrystallization. Yield 20% 
     (ii) Second Process 
     
       
         
         
             
             
         
       
     
     The di(cyclopentadienyl)molybdenum hexa-carbonyl complex (0.5 g, 1.02 mmol) and 0.6 g (5.08 mmol) of 3-sulphorane were dissolved in 50 ml of toluene and heated under reflux at 120° C. for 3 hours. After removing the solvent the yellow coloured product di(cyclopentadienyl) μ-oxodioxomolybdenum complex was produced and isolated from the reaction mixture by means of column chromatography. Yield 34% 
     Example 4 
     The synthesis of Compound I in the aforementioned Table 1, the case where X is S, Y is O and R 1  to R 10  are H. 
     
       
         
         
             
             
         
       
     
     Reaction in the same way as in Example 3 and the red coloured product di(cyclopentadienyl) μ-thioxodioxomolybdenum complex was isolated by means of column chromatography. Yield 14% 
     Example 5 
     The complex obtained in Example 2 was adjusted in such a way as to provide an Mo content of 500 ppm in engine oil (di-isononyl adipic acid) (viscosity at 100° C.: 3.04 mm 2 /s) to which 5% of a dispersing agent (alkenylsuccinic acid polyalkylene polyimide, trade name Infineum C9266) had been added. 
     Comparative Example 1 
     The case where the complex obtained in Example 2 had not been used in the composition of Example 5 was taken as Comparative Example 1. Both of the compositions are shown in Table 20 below. 
     These sample oils were subjected to 30 minute friction coefficient measurement and evaluation under the conditions shown in Table 19 below using an SRV tester (a reciprocating movement tester of the cylinder-on-disc type shown in  FIG. 2 ) and the results are shown in  FIG. 1 . The test piece was 52100 steel. 
     Testing Conditions 
     
       
         
           
               
               
               
             
               
                   
                 TABLE 19 
               
               
                   
                   
               
               
                   
                 Condition 
                 Parameter 
               
               
                   
                   
               
             
            
               
                   
                 Load 
                 400N 
               
            
           
           
               
               
               
               
            
               
                   
                 Frequency 
                 50 
                 Hz 
               
               
                   
                 Amplitude 
                 1.5 
                 mm 
               
               
                   
                 Temperature 
                 100° 
                 C. 
               
               
                   
                 Sample Size 
                 0.5 
                 mm 3   
               
               
                   
                   
               
            
           
         
       
     
     
       
         
           
               
               
               
             
               
                   
                 TABLE 20 
               
               
                   
                   
               
               
                   
                 Comparative 
                   
               
               
                   
                 Example 1 
                 Example 5 
               
               
                   
                   
               
             
            
               
                   
               
            
           
           
               
               
               
            
               
                 Base Oil 
                 Ester oil (di-isononyl 
                 Ester oil (di- 
               
               
                   
                 adipic acid) 
                 isononyl adipic 
               
               
                   
                   
                 acid) 
               
               
                 Friction-modifier 
                 Not added 
                 Complex obtained 
               
               
                   
                   
                 in Example 2 
               
               
                 Mo Content in the Oil ppm 
                 0 
                 500 
               
               
                 Alkenylsuccinic acid 
                 5 
                  5 
               
               
                 polyalkylene polyimide (%) 
               
               
                   
               
            
           
         
       
     
     The case of the Example 5 exhibited a low friction coefficient when compared with the base oil with no addition (Comparative Example 1) from 1 minute after the start of the test and it is clear that the compound had the function of a friction-modifier. That is to say, the compounding of a friction-modifier of this invention clearly shows a lower friction coefficient when compared with the case where it has not been compounded.