This invention relates to lubricants containing additives that enhance lubricity. There are only a few classes of compounds that qualify as high temperature fluids, that is, fluids used at temperatures above 300°C. A well known class of such fluids are the polyaryl ethers such as poiyphenyl ether. While these fluids have excellent stability, polyaryl ethers possess poor lubricity behavior. Hence, additives are needed to enhance lubricity of these fluids among other fluids without adversely effecting their stability. This invention, in one respect, is a lubricating composition which comprises a lubricating fluid and an aryl arenesulfonate in an amount sufficient to increase the lubricity of the lubricating fluid.

In another respect, this invention is a process for increasing the lubricity of a lubricating fluid which comprises adding an aryl arenesulfonate to the lubricating fluid in an amount greater than or equal to 0.5 percent and less than or equal to 5 percent based on the weight of the lubricating fluid.

The additives of this invention comprise aryl arenesuifonates. The aryl arenesulfonates contain one, two, or three sulfonate groups (-S0 ₃ -) wherein each sulfonate group is attached to two aryl groups. As defined herein, aryl arenesulfonates of this invention are of the formula AS0 ₃ A, AS0 ₃ BS0 ₃ A, or (AS0 ₃ ) ₃ B wherein A is independently in each occurrence phenyl or substituted phenyl, and wherein B is benzene or two benzene rings connected by a bridging group. Aryl areπedisulfonates can be of the formula AS0 ₃ Ph(XPh) _y S0 ₃ A wherein y is O or 1 and wherein X is a divalent bridging group such as C(CH ₃ ) ₂ , 0, OCH ₂ , OCH ₂ CH ₂ , OCH ₂ CH ₂ 0, C(CF ₃ ) ₂ , S, S0 ₂ , CO, and 9,9'-fluorene, preferably C(CH ₃ ) ₂ , 0, C(CF ₃ ) ₂ , S, SO,, CO, and 9,9'-fluorene. When B is benzene and the aryl arenesulfonate is a disulfonate, the SO.A groups can be attached in ortho, meta, or para arrangement. When B is two benzene rings connected by a bridging group, each benzene of B can be connected independently in meta or para arrangement. For all of the formulas above, when A is substituted phenyl, the phenyl can be substituted by halo, ketone, alkyl of uo to 10 carbons,

polyhaloalkyi, alkoxy, poiyhaloalkoxy, aryl, polyhaloaryi, aryioxy, polyhaloaryioxy, polyhaloalkylaryl, or polyhaloalkylaryloxy. The substituent of the phenyl group can be ortho, meta, or para to the sulfonate group. Preferred alkyl substituents contain up to 8 carbons. More preferred alkyl substituents include methyl, t-butyl, and 1 ,1 ,3,3-tetramethylbutyl. A

5 preferred polyhaloalkylaryl substituent is trifluoromethylphenyl. Preferred alkoxy substituents contain up to seven carbon atoms. More preferred aikoxy substituents include methoxy, n- butoxy, n-hexoxy, and n-heptoxy. Preferred aryl substituents include alkylphenyls, tri-t- butylphenyl, and halophenyls. A preferred halophenyl is fluorophenyl. Preferred poiyhaloalkoxy substituents include 1 ,1 ,3,3,3-pentafluoro-n-propoxy, 1 J , 2,3,3, 3-hexa- ι o fluoro-n-propoxy, and trifluoromethoxy. A preferred polyhaloalkyi is polyfluoroalkyi of less than eight carbon atoms, more preferably the polyhaloalkyi substituent is trifiuoromethyl. A preferred halo group is fluoro. Preferred aryioxy substituents are phenoxy and halophenoxy, more preferably phenoxy. Preferred ketone substituents include methyl ketone and phenyi ketone.

15

Examples of the aryl arenesulfonates of this invention are of Formula I:

wherein R is hydrogen, 4-methyl, 4-t-butyl, 4-methoxy, 4-n-butoxy, 4-phenoxy, 4- trifluoromethoxy, or 4-(1 , 1 ,3,3, 3-hexafluoro)-n-propoxy; R' is hydrogen, 4-t-butyl, 3-methoxy, 4-methoxy, 3-n-butoxy, 3-phenoxy, 4-(1 , 1 ,3,3-tetra methyl)butyl, 2-t-butyi, 4-n-heptoxy,

0

5

4-methyl, 2-t-butyl, 4-n-butoxy, 4-n-hexoxy, 3-methyl, 3-fluoro, 3-tπfluoromethyl, 4-methyl ketone, or 4-pheπyl ketone; of Formula II:

wherein R" is 3-methoxy, 3-trifluoromethyl, 3-phenoxy, 4-phenoxy, 4-(4-chloro)phenoxy, or 1 ,1 ,3,3-tetra-methylbutyl; of Formula III:

15 wherein R" isas defined above; of Formula IV:

wherein R'" is 1 ,1-dimethyipropyl, t-butyl, methoxy, n-butoxy, or phenoxy; of Formula V:

0

5

wherein R"- is n-butoxy; of Formula VI:

wherein ~? is hydrogen, t-butyl, n-butoxy; X is dimethylmethylene, ditrifluoromethylmethylene, oxygen, sulfur, SO., CO, or 9,9-fluorene; of Formula VII

-Λ-

wherein R' ¹ is t-butyl or n-Dutoxy; or of Formula VIII:

wherein R ^v " is 1 , 1 ,3,3-tetramethyIbutyl.

The most preferred aryl arenesulfonates of this invention possess high oxidation stability. The most preferred aryl arenesulfonates of this invention are aryl arenesulfonates of Formula I wherein R is hydrogen and R' is hydrogen, 4-t-butyl, 3-methoxy, or 3-phenoxy, or wherein R is 4-methyl and R' is hydrogen, 4-(1 , 1,3, 3-tetramethylbutyl), or wherein R is4-t-butyl and R' is hydrogen, 2-t-butyl, 4-t-butyl, 4-(1J, 3, 3-tetramethylbutyl), 3-methoxy, 3-n-butoxy, or wherein R is 4-methoxy and R' is hydrogen, 4-t-butyl, or 3-methoxy, or wherein R is -n-butoxy and R' is hydrogen or 3-phenoxy, or wherein R is 4-phenoxy and R' is hydrogen, 3-methyl, 4-t-butyl, 4-(1 ,1 ,3,3-tetramethyl-butyl), 3-fluoro, 3-trifluormethyl, 3-methoxy, 3-phenoxy, 4-phenyl ketone, or wherein R is 1 ,1 ,2,3,3,3-hexafluoro-n-propoxy and R' is 4-(1 ,1 ,3,3-tetramethyl butyl); or of Formula ll wherein R" is 3-methoxy, 3-trifluoromethoxy, 3-phenoxy, 4-phenoxy, 4-(4-chlorophenoxy), or 4-(1,1 ,3,3-tetra-methylbutyl); or of Formula III wherein R" is 4-(1, 1 ,3, 3-tetramethylbutyl) or 3-trifluoromethyl and X is O; or of the Formula IV wherein R" ¹ is 1 ,1-dimethyl-propyl, t-butyl, methoxy, or phenoxy; or of Formula VI wherein R ^v and X are as defined above; or of Formula VII wherein R ^ι is t-butyl; or of Formula VIII wherein R " is 1,1 ,3,S-tetramethyl butyl.

The aryl arenesulfonates of this invention are typically prepared by reacting an aryl sulfonyl chloride with phenol or substituted phenol under conditions effective to form the aryl arenesulfonate. This reaction is preferably carried out in the presence of an organic solvent, more preferably an anhydrous organic solvent. Examples of preferred solvents include pyridine, benzene, quinoline, diglyme, triethylamine, dimethyl sulfoxide, dimethyl formamide, n-methyl pyrrolidinone, N,N'-dimethyl acetamide, hexamethylphosphoramide, sulfolane, and toluene. An acid scavenger can also be used such as 4-dimethylarπinopyridine. The products of

the reaction are generally separated and purified by conventional techniαues sucn as chromatography.

Examples of aryl sulfonyl chlorides suitable as starting materials in the reaction to make aryl arenesulfonates of this invention include benzene sulfonyl chloride and benzene sulfonyl chlorides substituted by halo, ketone, alkyl of up to 10 carbons, polyhaloalkyi, alkoxy, poiyhaloalkoxy, aryl, polyhaioaryl, aryioxy, polyhaloaryloxy, polyhaloalkylaryl, or polyhaloalkylaryloxy groups. The substituent of the aryl sulfonyl chloride can be in ortho, meta, or para arrangement. When the aryl sulfonyl chloride is substituted by an alkyl group, preferred alkyls contain up to 8 carbons. More preferred alkyls include methyl, t-butyl, and 1,1,3,3-tetramethyl butyl. When the aryl sulfonyl chloride is substituted by an alkoxy group, preferred alkoxy groups contain upto seven carbon atoms. More preferred alkoxy groups include methoxy, n-butoxy, n-hexoxy, and n-heptoxy. Preferred aryl groups of an aryl sulfonyl chloride include aikylphenyls, tri-t-butylphenyl, and halophenyls such as fluorophenyl. Preferred poiyhaloalkoxy groups of an aryl sulfonyl chloride include 1 , 1 ,3,3,3-pentafluoro-n-propoxy, 1,1 , 2,3,3, 3-hexafluoro-n-propoxy, and trifluoromethoxy. A preferred polyhaloalkyi is trifluoromethyl. A preferred halo group is fluoro. A preferred aryioxy group of an aryl sulfonyl chloride is phenoxy. Preferred ketone groups include methyl ketone and phenyl ketone. More preferred aryl sulfonyl chlorides are benzene sulfonyl chlorides substituted by 3-methyl, 4-methyl, 2-t-butyl, 4-t-butyl, 4-(1,1 ,3,3-tetra-methyl)butyl, 3-trifluoromethyl, 3-methoxy, 4-methoxy, 3-n-butoxy, 4-n-butoxy, 4-n-hexoxy, 4-n-heptoxy, 4-trifluoromethoxy, 4-(1 ,1 ,2,3,3,3-hexa-fluoro)-n-propoxy, 3-phenoxy, 4-phenoxy, 3-fluoro, 4-methyl ketone, or 4-phenyi ketone groups. If an aryl arenedisulfonate is desired, the disulfonate can be produced by employing either a benzenediol such as 1 ,4-benzenediol and 1 ,3-benzenediol or by using as a starting material a benzene disulfonyl chloride such as 1,3-benzene disulfonyl chloride and 1 ,4-benzene disulfonyl chloride. Similarly, when "B" represents two benzene rings linked by a bridging group, the starting material can be a diol or disulfonyl chloride of "B". Likewise, when an aryl arenetrisuifonate is desired, the trisulfonate can be produced by employing either a benzenetriol, described hereinbelow, or by using as a starting material a trisulfonyl chloride such as 1 ,3,5-benzene trisulfonyl chloride. Examples of phenols suitable as starting material in the reaction to make aryl arenesulfonates of this invention include phenol, substituted phenol, 1,4-benzenediol, 1,3-behzenediol, and 1 ,3,5-benzenetriol. Examples of substituted phenols include phenol substituted by halo, ketone, alkyl of up to 10 carbons, polyhaloalkyi, alkoxy, poiyhaloalkoxy, aryl, polyhaioaryl, aryioxy, polyhaloaryloxy, polyhaloalkylaryl, or polyhaloalkylaryloxy groups. The substituted phenol can be of ortho, meta, or para arrangement. When the substituted phenol is substituted by an alkyl group, preferred alkyls contain up to 8 carbons. More preferred alkyls include methyl, t-butyl, and 1 , 1 ,3, 3-tetramethylbutyl. When the substituted phenol is substituted by an alkoxy group, preferred alkoxy groups contain up to seven carbon

atoms. More preferred alkoxy groups include methoxy, n-butoxy, n-hexoxy, and n-heptoxy. Preferred aryl groups of a substituted phenol include aikylphenyis, tri-t-butylphenyl, and halophenyls such as fluorophenyl. Preferred poiyhaloalkoxy groups of a substituted phenol include 1 ,1,3,3,3-pentafluoro-n-propoxy, 1 , 1 ,2,3,3,3-hexafluoro-n-propoxy, and trifluoromethoxy. A preferred polyhaloalkyi is trifluoromethyl. A preferred halo group is fluoro. A preferred aryioxy group of a substituted phenol is phenoxy. Preferred ketone groups include methyl ketone and phenyl ketone. More preferred substituted phenols are phenols substituted by 3-methyl, 4-methyl, 2-t-butyl, 4-t-butyl, 4-(1 , 1 ,3,3-tetra-methyl)butyl, 3- trifiuoromethyl, 3-methoxy, 4-methoxy, 3-n-butoxy, 4-n-butoxy, 4-n-hexoxy, 4-n-heptoxy, 4-trifluoromethoxy, 4-(1, 1,2,3,3, 3-hexa-fluoro)-n-propoxy, 3-phenoxy, 4-phenoxy, 3-fluoro, 4-methyl ketone, or 4-phenyl ketone groups.

The aryl arenesulfonates of this invention are used as lubricity-enhancing additives for lubricating fluids in a lubricant composition. As defined herein, lubricating fluids include polyaryl ether fluids, hydrocarbon lubricants such as mineral oil, alpha-oiefin fluids, silicone fluids and greases, polyalkyi ether fluids, perfluoroalkylpolyether fluids and greases, ester lubricants such as pentaerythritol esters and trimethylol alkane esters, and phosphazene fluids. Most preferably, the lubricating fluid is a polyaryl ether. Examples of polyaryl ethers include para and meta forms of bis(phenoxy-phenoxy) benzene (known as "5P4E"), para and meta forms of bis(phenoxyphenyl) ether (known as "4P3E"), and para and meta forms of phenoxy-phenoxy benzene (known as "3P2E").

The aryl arenesulfonates are employed in the lubricant composition in an amount sufficient to increase the lubricity of the lubricating fluid. Preferably, the aryl arenesulfonates are employed in a concentration, based on the weight of the lubricating fluid component, of greater than or equal to 0.1 percent, more preferably greater than or equal to 0.5 percent, and most preferably greater than or equal to 1 percent; and preferably less than or equal to 20 percent, more preferably less than or equal to 10 percent, and most preferably less than or equal to 5 percent. To prepare a solution of the aryl arenesulfonates in the lubricant composition, it is preferable to first dissolve the compound in an organic solvent such as, for example, methylene chloride, and to mix this solution with a solution of the lubricant composition in an organic solvent. The mixture Is then preferably filtered to remove solid impurities and any solvents are evaporated from the mixture.

The aryl arenesulfonates of this invention provide a lubricant composition with enhanced lubricity, relative to lubricant or heat-transfer systems which do not contain such compounds. Such compounds are especially useful as additives in high temperature lubricant basestocks which may have the thermal and oxidative stability to withstand high temperature applications, such as in jet aircraft engines, but which have lubricating properties which are iess than desired. An example of such a lubricant basestock is a polyarylether fluid. The lubricity of lubricant compositions may be measured by applying a standard test method as described in

ASTM D-2783, "Standard Method for Measurement of Extreme Pressure Properties of Lubricating Fluids (Four-ball Method)." In addition, the aryl arenesulfonates of this invention are advantageously thermally and oxidatively stable when used in high temperature applications, and are advantageously soluble when used in such systems. The aryl arenesulfonates increase lubricity of polyaryl ethers. For example, the lubricity of 5P4E polyphenyl ether fluid is increased greater than 20 percent, preferably greater than 30 percent, when bis[3-phenoxy)phenyl] 1 ,3-benzenedisulfonate is added at 1 weight percent loading, lubricity being measured by the standard ASTM Four-Ball method at 300°C, 15 Kg load, on M50 steel balls, for one hour at 1200 rpm. As used herein, lubricity is measured by o this ASTM Four-Ball method.

The following examples are given to illustrate the invention and should not be interpreted as limiting it in any way. Unless stated otherwise, all parts and percentages are given by weight. All reactions requiring anhydrous conditions are performed in oven-dried glassware which was cooled under nitrogen. Thinjayer chromatography (TLC) is performed on 5 glass plates precoated with 0.25 mm of silica gel (Analtech, Inc., silica gel GHLF). Flash chromatography is performed on 230-400 mesh siiica gel 60. Melting points are determined in open capillary tubes, and are uncorrected.

EXAMPLE 1 : Preparation of Bis[3-(phenoxy)phenvn 1 ,3--benzenedisulfonate

All apparatus is rigorously dried and flushed with nitrogen before use. The reaction is performed in a 25 ml flask equipped with a magnetic stirring bar and a CaCI ₂ drying tube. The flask is charged with benzene- 1 ,3-disulfonyl chloride (2.75 grams, 10 mmol), 3-phenoxyphenol (3.72 grams, 20 mmol), and 4-dimethyl-

-aminopyridine (60mg, 0.5 mmol), and anhydrous pyridine (10 ml). The mixture is stirred for 2 hours at ambient temperature. The product is separated by admixing the mixture with water (20 ml) and ethyl ether (30 ml), isolating the organic phase and washing with 25 ml portions of 5 percent HCI (3x), water, 5 percent NaOH, water, and saturated brine, then drying with MgSO . The organic phase is filtered and is concentrated to leave 3.04 grams of a thick yellow oil. The yellow oil is purified by column chromatography using flash grade silica gel and using 1 : 1 pentane-CH ₂ CI ₂ initially and then CH ₂ CI ₂ as the eLuent. An almost colorless, viscous oil is obtained (2.99 grams, 52 percent yield) of the title compound.

A yield of 84 percent is obtained at 3 times the above scale when the mixture is heated at reflux for 20 hours.

EXAMPLE 2: Preparation of 4-( 1,1 ,3, 3-Tetramethyl-butyl)phenyl Λ tert- butvQbenzenesulfoπate

An oven-dried 50 ml 3-necked flask is equipped with a magnetic stirring Dar and a CaCI ₂ drying tube and is charged with 4-ter -butylsulfonyl chloride (7 grams, 30 mmol),

-(1 ,1 ,3,3-tetramethylbutyl)phenol (6.2 grams, 30 mmoi), 4-dimethylamιnopyridine (0.18 gram. 1.5 mmol), and anhydrous pyπoine (20 ml). The mixture is stirred at ambient temperature for 24 hours, then a reflux condenser is attached, and the mixture is heated at reflux for 1 hour. Workup consists of partitioning the mixture between Et.O and H,0 (75 ml each), and washing the organic phase successively with 50 ml portions of H ₂ 0(2x), 5 percent HCI (2x), H ₂ 0 (2x), 5 percent NaOH, H ₂ 0 (2x), and brine, then drying (MgSO _j ), filtration and concentration. An amber oil (10.63 grams) is recovered. On standing, a crystalline solid is formed. After recrystallization from hexane, collecting three crops, and a subsequent recrystallization of the combined crops, 5.64 grams (47 percent yield) of the title compound is recovered as white prisms, m.p. 68°C to 71°C.

EXAMPLE 3: Preparation of Bis[3-trifluoromethyl)phenvπ 1 ,3-benzenedisulfonate

An oven-dried 50 ml 3-necked flask is equipped with a magnetic stirring bar and a CaCI ₂ drying tube and is charged with benzene- 1 ,3-disulfonyl chloride (6.9 grams, 25 mmol), α, α, α-trifluoro-m-cresol (6.1 ml, 50 mmol), and 4-dimethylaminopyridine (0.15 gram, 1.25 mmol), and anhydrous pyridine (20 mi) is added. The mixture is stirred at ambienttemperature for 24 hours, then a reflux condenser is attached, and the mixture is heated at reflux for 1 hour. Workup consists of partitioning the mixture between Et ₂ 0 and H ₂ 0 (100 ml each), washing the organic phase successively with 50 ml portions of H ₂ 0 (2x), 5 percent HCI (2x), H ₂ 0, 5 percent NaOH, H ₂ 0 (2x), and brine, then drying (MgS0 ₄ ), filtration and concentration. A pale yellow oily residue (7.06 grams) is collected. HPLC analysis on a reverse phase column shows the product to contain a small amount of residual α,α , α-trifluoro-m-cresol. The latter is effectively removed by steam distillation on the rotavap to give 6.72 grams (50 percent yield) of the pure title compound as a pale yellow oil.

When this run is repeated on the same scale and under similar conditions, except that the reaction mixture is heated at reflux for 20 hours, the crude oily product obtained after workup crystallized on standing, and is recrystallized from MeOH-H ₂ 0 (9: 1) to give 10.7 grams (81 percent yield) of white prisms, m.p. 59°C to 60°C.

EXAMPLE 4: Preparation of bis[4-(4-chlorophenoxy)phenyJl 1 ,3-Benzenedisulfonate

A 1 liter 3-necked flask is equipped with a mechanical stirrer, a Dean-Stark trap carrying a reflux condenser, and a heating mantle, and is charged with 4-methoxyphenol (35.9 grams, 0.29 mol), 85 percent KOH (19.1 grams, 0.29 mol),and p-xylene (350 ml). The mixture is heated at reflux for 1 hour, removing the water of reaction azeotropically. Then it is cooled, and 1 -chloro-4-iodobenzene (69 grams, 0.29 mol), copper powder (2.9 grams, 46 mmol), and cuprous chloride (2.9 grams, 29 mmol) are added, and the mixture is heated at reflux for 20 hours. Workup consists of diluting the cooied mixture with Et ₂ 0 (200 ml), filtration tnrough a

medium-fritted funnel, and concentration of the filtrate to leave a deep dark oiiy residue. This crude material, consisting primarily of 4-(4-chlorophenoxy)anisole, is treated with glacial acetic acid (275 ml) and 48 percent HBr (105 ml), then the mixture is heated at reflux for 24 hours. Workup consists of partitioning the mixture between H.,0 (1.2 1) and CH.CL, (0.5 I), washing the

5 organic phase with H ₂ 0 (0.5 I), and concentration to leave a deep dark oily residue. This residue is taken up in ethanol (0.5 I) and treated with activated carbon (Norit; ca. 50 grams). Filtration through celite, and concentration of the filtrate gave the crude title compound as a thick, red oil. Further purification of the product is achieved by chromatography on a column packed with flash-grade silica gel (6" x 2" i.d.), eluting with CH ₂ CL ₂ , to give after concentration a

1 o pinkish solid, which is subsequently recrystallized from hexane-EtOAc to give 31.4 grams (49 percent yield) of pure 4-(4-chlorophenoxy)phenol as off-white prisms, m.p. 85°C to 86°C.

A 100 ml 3-necked oven-dried flask equipped with a magnetic stirring bar and a CaCI ₂ -Drierite drying tube is charged with 1 ,3-benzenedisuifonyl chloride (4.3 g, 15.6 mmol), 4- (4-chlorophenoxy)phenol (7 g, 31.7 mmol, 4-dimethylaminopyridine (0.38 g, 3.1 mmol), and

15 anhydrous pyridine (35 ml). The mixture is stirred at ambient temperature for 18 hours, then is partitioned between 0% FHCI (300 ml) and methylene chloride (100 ml), and the organic phase is washed with water (100 ml) and brine (100 ml), dried (MgSo ₄ ), filtered and concentrated to leave a thick yellowish oily residue. This material is chromatographed on a column packed with flash-grade silica gel (8"x2" i.d.), eluting initially with pentane-methylene

20 chloride (4: 1 , v/v), then with methylene chloride. This gave 9.1 g (91 % yield) of the title compound in high purity as a thick, clear, faintly yellowish oil, which turned glassy on standing.

EXAMPLE 5: Preparation of 1 ■3-Bisf4-methoxybenzene-sulfonyloxy1benzene

A 25 ml 3-necked flask is equipped with a magnetic stirring bar and a reflux condenser fitted with a CaCI ₂ drying tube and is charged with resorcinol (2.9 grams, 27 mmol),

25 4-methoxybenzenesulfonyl chloride (12.1 grams, 58 mmol), pyridine (20 ml), and 4-dimethylaminopyridine (0.2 gram, 1.3 mmol). The stirred mixture is heated at reflux for 10 hours, then is stirred at ambient temperature for 24 hours. Workup consists of partitioning the mixture between Et ₂ 0 and H ₂ 0 (50ml each), washing the organic phase successively with 50ml portions of H ₂ 0, 5 percent HCI (2x), H.,0, 5 percent NaOH, H ₂ 0, and brine, drying (MgS0 ),

30 filtration and concentration. This gives 10.5 grams of an amber oil. A crystalline solid is formed by treating with methanol at ambient temperature. Recrystallization twice from MeOH gives 8.8 grams (73 percent yield) of the title compound as white needles, m.p. 81 °C to 84°C.

EXAMPLE 6: Preparation of 2.2-Bis[4-(benzene-sulfonyloxy)phenyl]propane ~- An oven-dried 100 ml 3-necked flask is equipped with a magnetic stirring bar, a reflux condenser carrying a CaCI,-Drierite drying tube, and a heating mantle, and is charged with 4,4'-isopropylidenediphenol (4.5 grams, 19.7 mmol), 4-dimethyiaminopyridine (0.48 gram,

3.93 mmol), and anhydrous Et.N (40 ml). The solution is stirred ano treated slowly with - benzenesulfonyl chloride (5.7mL, 44.7 mmol) via syringe. The resulting mixture is heated at reflux for 9 hours. Workup consists of partitioning the reaction mixture between H ₂ CI ₂ (100 ml) and a mixture of water (150 ml) and concentrated HCI (40 ml), then washing the organic phase successively with 100 ml portions of water, 5 percent NaOH, water, and saturated brine. Drying (MgS0 ₄ ), filtration and concentration gives 10.6 grams of a deep dark oily residue. TLC analysis on silica gel shows one major component (R ₍ = 0.45; CH„CI ₂ ), and some minor more polar components. Chromatography on a column packed with flash-grade silica gel (6" x 1 " i.d.), eluting with CH ₂ CI ₂ , gives 9.71 grams of a yellow oil. Crystallization from EtOAc-MeOH- 0 H.O (20 ml M OO ml: 10 ml), using seed crystals obtained from a micro-crystallization on a small sample, affords 8.35 grams (83.5 percent yield) of the title compound as a white crystalline solid, m.p. 92°C to 93°C

EXAMPLE 7: Preparation of 2,2-Bisf4-(benzenesulfonyl-oxy)phenvn-

1 , 1 ,1 ,3,3,3-hexafluoropropane 5

An oven-dried 100 ml 3-necked flask is equipped with a magnetic stirring bar, a reflux condenser carrying a CaCI ₂ -Drierite drying tube, and a heating mantle, and is charged with 4,4'-(hexafluoro-isopropylidene)diphenol (Aldrich) (5.45 grams, 16.2 mmol), 4- dimethylaminopyridine (0.4 gram, 3.3 mmol), and anhydrous Et ₃ N (40 ml). The solution is stirred and treated slowly with benzenesulfonyl chloride (4.7 ml, 36.8 mmol) via syringe. The 0 resulting mixture is heated at reflux for 9 hours. Workup consists of partitioning the reaction mixture between CH -Cl, (100 ml) and a mixture of H.O (150 ml) and concentrated HCI (40 ml), washing the organic phase successively with 100 ml portions of H ₂ 0, 5 percent NaOH, H ₂ 0, and saturated brine, drying (MgSOJ, filtration and concentration. This gives 10.6 grams of a reddish oily residue. TLC analysis on siiica gel shows one main component (R, = 0.54; CH ₂ CI ₂ ). 5 Chromatography on a column packed with flash-grade siiica gel (3" x 1 " i.d.), eluting with CH ₂ CI ₂ , gives 9.32 grams of a faintly yellowish oil, which solidifies on standing. Recrystallization from EtOAc-MeOH-H.,0 (20 ml : 100 ml: 10 ml)affords 8.91 grams (89 percent yield) of the title compound as a white crystalline solid, m.p. 133°C to 134°C.

- EXAMPLE 8: Preparation of 2,2-Bi9f4-(4-tert--butyibenzenesulfonvtoxy) phenyllpropane

An oven-dried 50 ml 3-necked flask is equipped with a magnetic stirring bar and reflux condenser carrying a CaCI ₂ drying tube and is charged with 4-ter -butylbenzenesulfonyl chloride 9.3 grams (40 mmol), 4,4'-isopropylidenediphenol (4.1 1 grams, 18 mmol), 5 4-dimethylaminopyridine (0.1 1 gram, 0.9 mmol), and anhydrous pyridine (20 ml), and the

mixture is stirred and heated at reflux for 14 hours. Workup consists of partitioning the mixture between Et.O and H ₂ O (50 ml each), washing the organic phase successively with 100 ml portions of H ₂ 0 (2x), 5 percent HCI (2x), H.,0, saturated (2x), H ₂ 0 and brine, then drying (MgS0 ₄ ), filtration and concentration. This gives 10.41 grams of a pale yellow sold. Three consecutive recrystallizations from EtOH-MeOH (2: 1 ) affords 7.87 grams (70 percent yield) of the title compound as white prisms, m.p. 124°Cto 127°C.

EXAMPLE 9: Preparation of 2,2-Bis[4-(4-tert-butyl-benzenesulfonyloxy)phenvn-1 , 1 ,1 , 3,3,3- hexafluoropropane

An oven-dried 50 ml 3-necked flask is equipped with a magnetic stirring bar and a reflux condenser carrying a CaCI ₂ drying tube and is charged with 4- tert-butyl benzenesulfonyl chloride 8.14 grams (35 mmol), 4,4'-hexafiuoroisopropylidenediphenol (5.37 grams, 16 mmol), 4-dimethylaminopyridine (0.1 grams, 0.8 mmol), and anhydrous pyridine (20 ml), and the mixture is stirred and heated at reflux for 15 hours. Workup consists of partitioning the mixture between E ,O and H ₂ O (50 m! each), washing the organic phase successively with 100 ml portions of H ₂ 0, 5 percent HCI, H.O, saturated NaHC0 ₃ , H.,0 and brine, then drying (MgS0 ₄ ), filtration and concentration. This gives 10.03 grams of a pale yellow oil. Crystallization from EtOH-MeOH (2: 1) affords 7.53 grams (64 percent yield) of the title compound as white prisms, m.p. 177°C to 180°C.

EXAMPLE 10: Preparation of Bisf4-(benzenesutfonyl-oxy)phenyl1 Ether

An oven-dried 100 ml 3-necked flask is equipped with a magnetic stirring bar, a reflux condenser carrying a CaCI ₂ -Drierite drying tube, and a heating mantle, and is charged with 4,4'-oxydi phenol (Pfaltz & Bauer) (4.2 grams, 20.8 mmol), 4-dimethylaminopyridιne (0.5 gram, 4.1 mmol), and anhydrous Et ₃ N (40 ml), and the stirred solution is treated slowly with benzenesulfonyl chloride (6 ml, 47 mmol) via syringe. The resulting mixture is heated at reflux for 9 hours. Workup consists of partitioning the reaction mixture between CH ₂ CI ₂ (100 ml) and a mixture of water (150 ml) and concentrated HCI (40 ml), then washing the organic phase successively with 100 ml portions of water, 5 percent NaOH, water, and saturated brine. Drying (MgS0 ), filtration and concentration gives a red _. oily residue. TLC analysis on silica gel shows one major component (R _f = 0.36; CH ₂ CI ₂ ), and some minor more polar components.

Chromatography on a column packed with flash-grade silica gel (6" x 1 " i.d.), eluting with CH ₂ G ₂ , gives 7.64 grams of a faintly yellowish oil, which solidifies on standing. Recrystallization from a mixture of EtOAc (20 ml) and water (10 ml) affords 6.23 grams (62 percent yield) of the title compound as a white crystalline solid, m.p. 129°C to 130°C.

EXAMPLE 1 1 : Preparation of Bisf4-(benzenesulfonyl-oxy)phenvn Sulfide

A 100 ml 3-necked oven-dried flask is equipped with a magnetic stirring bar and a CaCI ₂ -Drierite drying tube and is charged with 4,4'-thiodiphenol (5.3 grams, 24.3 mmol),

benzenesulfonyl chloride (6.5 ml, 50.9 mmol), 4-dimethylaminopyπdene (0.59 grams, 4.8 mmol), and anhydrous pyridine (40 ml). The mixture is stirred at ambient temperature for 18 hours, and at reflux for 4 hours, then is poured into ice-cold water (100 ml) with vigorous stirring, and the yellow oil that separates is extracted into CH ₂ CI ₂ (100 ml), and washed with water (100 ml). Drying (MgS0 ₄ ), filtration and concentration affords a yellow oil. Purification by filtration through a column packed with flash-grade silica gel (5" x 2" i.d.), eluting with CH ₂ CI ₂ (ca. 0.51), gives after solvent removal under vacuum 11.8 grams (98 percent yield) of the title compound as a faintly yellowish, thick glass material.

EXAMPLE 12: Preparation of 9,9-Bis[4-(benzenesulfonyl-oxy)phenyl]fluorene 0

An oven-dried 100 ml 3-necked flask is equipped with a magnetic stirring bar, a reflux condenser carrying a CaCI ₂ -Drierite drying tube, and a heating mantle, and is charged with 9,9-bis(4-hydroxyphenyl)-fluorene (3 grams, 16.1 mmol), 4-dimethylaminopyridine (0.4 gram, 3.3 mmol), and anhydrous pyridine (35 ml). The solution is stirred and treated slowly with benzenesulfonyl chloride (4.7 ml, 36.8 mmol) via syringe. The resulting mixture is heated 5 at reflux for 16 hours, then is poured into water (200 ml) with vigorous stirring, resulting in the separation of a gummy white solid. The supernatant aqueous liquid is decanted, and the solid is taken up in CH ₂ CI ₂ (100 ml) and washed successively with 100 ml portions of 5 percent HCI, water and saturated brine, then is dried (MgS0 ₄ ), filtered and concentrated to leave a white solid. Recrystallization from Hexane-EtOAc affords 7.55 grams (74 percent yield) of the title 0 compound as white fluffy crystals, m.p. 225°C to 225.5°C.

EXAMPLE 13: Preparation and Evaluation of Mixtures of Polyaryl Ether and Various

Disulfonate Additives A formulation of 5P4E polyphenyl ether fluid containing 1 weight percent of the ⁵ disulfonate of Example 1 is evaluated for lubricity using the ASTM Four-Ball method at 300°C, 15 Kg load, on M50 steel balls, for 1 hour at 1200 rpm. This formulation exhibited reduced wear on the balls as compared with an identical evaluation using 5P4E polyphenyl ether containing no additive. In a control run with no additive, a wear scar diameter (in millimeters) of 2.36 and a coefficient of 0.19 is observed. Wear reduction percentages of the additives is ⁿ calculated as the percentage decrease in wear scar diameter relative to the control run ([100 X (2.36 - wear scar diameter when an additive is present)/2.36]). When the disulfonate of ^■ Example 1 is employed as the additive, a 33 percent wear reduction is observed based on a wear scar diameter of 1.58. When the disulfonate of Example 3 is employed as the additive, a 22 percent wear reduction is observed based on a wear scar diameter of 1.83. When the ^ disulfonate of Example 6 is employed as the additi e, a 15 percent wear reduction is observed based on a wear scar diameter of 2.01 . When the disulfonate of Example 7 is employed as the additive, a 6 percent wear reduction is observed based on a wear scar diameter of 2.21. When

the disulfonate of Example 10 is employed, a 17 percent wear reduction is oDserveα baseα on a wear scar diameter of 1.97.