GB2421503A - Preparation of thiobisphenols from alkylphenols from natural sources - Google Patents
Preparation of thiobisphenols from alkylphenols from natural sources Download PDFInfo
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- GB2421503A GB2421503A GB0422039A GB0422039A GB2421503A GB 2421503 A GB2421503 A GB 2421503A GB 0422039 A GB0422039 A GB 0422039A GB 0422039 A GB0422039 A GB 0422039A GB 2421503 A GB2421503 A GB 2421503A
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- GB
- United Kingdom
- Prior art keywords
- thiobisphenols
- sulphur
- cardanol
- reaction
- prepared
- Prior art date
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- PTFIPECGHSYQNR-UHFFFAOYSA-N cardanol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1 PTFIPECGHSYQNR-UHFFFAOYSA-N 0.000 claims abstract description 41
- JOLVYUIAMRUBRK-UTOQUPLUSA-N Cardanol Chemical compound OC1=CC=CC(CCCCCCC\C=C/C\C=C/CC=C)=C1 JOLVYUIAMRUBRK-UTOQUPLUSA-N 0.000 claims abstract description 21
- HWIKMSXIILZULT-UHFFFAOYSA-N 3-undecylphenol Chemical compound CCCCCCCCCCCC1=CC=CC(O)=C1 HWIKMSXIILZULT-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- JOLVYUIAMRUBRK-UHFFFAOYSA-N 11',12',14',15'-Tetradehydro(Z,Z-)-3-(8-Pentadecenyl)phenol Natural products OC1=CC=CC(CCCCCCCC=CCC=CCC=C)=C1 JOLVYUIAMRUBRK-UHFFFAOYSA-N 0.000 claims abstract description 14
- YLKVIMNNMLKUGJ-UHFFFAOYSA-N 3-Delta8-pentadecenylphenol Natural products CCCCCCC=CCCCCCCCC1=CC=CC(O)=C1 YLKVIMNNMLKUGJ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 244000226021 Anacardium occidentale Species 0.000 claims abstract description 14
- FAYVLNWNMNHXGA-UHFFFAOYSA-N Cardanoldiene Natural products CCCC=CCC=CCCCCCCCC1=CC=CC(O)=C1 FAYVLNWNMNHXGA-UHFFFAOYSA-N 0.000 claims abstract description 14
- FWMUJAIKEJWSSY-UHFFFAOYSA-N sulfur dichloride Chemical compound ClSCl FWMUJAIKEJWSSY-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 239000000654 additive Substances 0.000 claims abstract description 7
- 235000001274 Anacardium occidentale Nutrition 0.000 claims abstract description 6
- 239000010687 lubricating oil Substances 0.000 claims abstract description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 16
- 239000005864 Sulphur Substances 0.000 claims description 16
- 230000015572 biosynthetic process Effects 0.000 claims description 12
- 238000003786 synthesis reaction Methods 0.000 claims description 11
- 235000020226 cashew nut Nutrition 0.000 claims description 9
- 150000002989 phenols Chemical class 0.000 claims description 9
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- 241000693997 Anacardium Species 0.000 claims 1
- 235000001271 Anacardium Nutrition 0.000 claims 1
- 230000009466 transformation Effects 0.000 claims 1
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 abstract description 26
- 239000000203 mixture Substances 0.000 abstract description 20
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract description 15
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 abstract description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 abstract description 9
- -1 3-pentadecylphenol (hydrogenated cardanol Chemical class 0.000 abstract description 5
- YLKVIMNNMLKUGJ-BQYQJAHWSA-N Cardanolmonoene Chemical compound CCCCCC\C=C\CCCCCCCC1=CC=CC(O)=C1 YLKVIMNNMLKUGJ-BQYQJAHWSA-N 0.000 abstract description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 5
- 239000003208 petroleum Substances 0.000 abstract description 5
- KWYIZCAVXFLWSZ-UHFFFAOYSA-N 2-hydroxy-6-undecylbenzoic acid Chemical compound CCCCCCCCCCCC1=CC=CC(O)=C1C(O)=O KWYIZCAVXFLWSZ-UHFFFAOYSA-N 0.000 abstract description 4
- 235000003246 Anacardium giganteum Nutrition 0.000 abstract description 4
- 244000005248 Anacardium giganteum Species 0.000 abstract description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 3
- 239000002904 solvent Substances 0.000 abstract description 3
- 238000006114 decarboxylation reaction Methods 0.000 abstract description 2
- 239000002803 fossil fuel Substances 0.000 abstract description 2
- 229910052742 iron Inorganic materials 0.000 abstract description 2
- 150000003568 thioethers Chemical class 0.000 abstract 2
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 238000005984 hydrogenation reaction Methods 0.000 abstract 1
- FIQMHBFVRAXMOP-UHFFFAOYSA-N triphenylphosphane oxide Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)(=O)C1=CC=CC=C1 FIQMHBFVRAXMOP-UHFFFAOYSA-N 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- VWGKEVWFBOUAND-UHFFFAOYSA-N 4,4'-thiodiphenol Chemical compound C1=CC(O)=CC=C1SC1=CC=C(O)C=C1 VWGKEVWFBOUAND-UHFFFAOYSA-N 0.000 description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- SKCNIGRBPJIUBQ-UHFFFAOYSA-N chloroform;ethyl acetate Chemical compound ClC(Cl)Cl.CCOC(C)=O SKCNIGRBPJIUBQ-UHFFFAOYSA-N 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N ethyl acetate Substances CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 4
- 239000000543 intermediate Substances 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- BLDLRWQLBOJPEB-UHFFFAOYSA-N 2-(2-hydroxyphenyl)sulfanylphenol Chemical compound OC1=CC=CC=C1SC1=CC=CC=C1O BLDLRWQLBOJPEB-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000003818 flash chromatography Methods 0.000 description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- KVVSCMOUFCNCGX-UHFFFAOYSA-N cardol Chemical compound CCCCCCCCCCCCCCCC1=CC(O)=CC(O)=C1 KVVSCMOUFCNCGX-UHFFFAOYSA-N 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- SZBYVOSSTHEBFR-UHFFFAOYSA-N 2-(2-methyloctan-2-yl)phenol Chemical compound CCCCCCC(C)(C)C1=CC=CC=C1O SZBYVOSSTHEBFR-UHFFFAOYSA-N 0.000 description 1
- IJWXCYSPVNCDMA-UHFFFAOYSA-N 4-(2-methyloctan-2-yl)phenol Chemical compound CCCCCCC(C)(C)C1=CC=C(O)C=C1 IJWXCYSPVNCDMA-UHFFFAOYSA-N 0.000 description 1
- ISAVYTVYFVQUDY-UHFFFAOYSA-N 4-tert-Octylphenol Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(O)C=C1 ISAVYTVYFVQUDY-UHFFFAOYSA-N 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- KAOMOVYHGLSFHQ-UTOQUPLUSA-N anacardic acid Chemical compound CCC\C=C/C\C=C/CCCCCCCC1=CC=CC(O)=C1C(O)=O KAOMOVYHGLSFHQ-UTOQUPLUSA-N 0.000 description 1
- 235000014398 anacardic acid Nutrition 0.000 description 1
- ADFWQBGTDJIESE-UHFFFAOYSA-N anacardic acid 15:0 Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1C(O)=O ADFWQBGTDJIESE-UHFFFAOYSA-N 0.000 description 1
- 230000009172 bursting Effects 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- UFMJCOLGRWKUKO-UHFFFAOYSA-N cardol diene Natural products CCCC=CCC=CCCCCCCCC1=CC(O)=CC(O)=C1 UFMJCOLGRWKUKO-UHFFFAOYSA-N 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000013375 chromatographic separation Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 description 1
- 229910000071 diazene Inorganic materials 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 230000003467 diminishing effect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229940093499 ethyl acetate Drugs 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000003879 lubricant additive Substances 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 235000014571 nuts Nutrition 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000010399 physical interaction Effects 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000005671 trienes Chemical class 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
- C07C323/10—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton
- C07C323/18—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton
- C07C323/20—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton with singly-bound oxygen atoms bound to carbon atoms of the same non-condensed six-membered aromatic ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D319/00—Heterocyclic compounds containing six-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D319/10—1,4-Dioxanes; Hydrogenated 1,4-dioxanes
- C07D319/14—1,4-Dioxanes; Hydrogenated 1,4-dioxanes condensed with carbocyclic rings or ring systems
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
- C10M135/20—Thiols; Sulfides; Polysulfides
- C10M135/28—Thiols; Sulfides; Polysulfides containing sulfur atoms bound to a carbon atom of a six-membered aromatic ring
- C10M135/30—Thiols; Sulfides; Polysulfides containing sulfur atoms bound to a carbon atom of a six-membered aromatic ring containing hydroxy groups; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
- C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
- C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
- C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
- C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
- C10M2219/088—Neutral salts
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/64—Environmental friendly compositions
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Thiobisphenols may be prepared by the reaction of 3-pentadecylphenol (hydrogenated cardanol) or 3-undecylphenol (anagigantol) with sulfur dichloride. 3-Pentadecylphenol may be prepared by hydrogenation of cardanol obtained from Anacardium occidentale, while 3-undecylphenol may be prepared by catalytic decarboxylation of anagigantic acid obtained from Anacardium giganteum. These reactions afford a mixture of di-(4-hydroxy-2-alkylphenyl)sulphides and di-(2-hydroxy-4-alkylphenyl)sulphides, in which the former predominates. Suitable solvents include benzene, light petroleum, n-hexane, chloroform and acetonitrile. A catalyst selected from anhydrous aluminium chloride, iron and triphenylphosphine oxide may also be utilised. Thiobisphenols may also be prepared from cardanol and cardanol monoene using this process. The use of other 2-, 3- or 4-alkylphenols is also envisaged. The thio-bisphenols prepared by this process are useful as extreme pressure type additives in lubricating oils as an alternative to such materials prepared from t-octyl or 4-t-nonylphenols from fossil fuel petroleum resources.
Description
BRITISH PATENT SPECIFICATION
The synthesis of isomeric thiobisphenols, di-(4_hydroxy..2...allefl) yJpheflyl) suiphide and di(2hydroxy..4..aJk(efl)y1Pheflyl)sulphjd from renewable phenolic lipid resources as lubricant additives This invention describes the synthesis of isomeric thiobisphenols from phenolic compounds derived from the natural phenolic resources occurring in Anacardium occidentale (cashew) and in the related Anacardium giganteum, by reaction with sulphur dichiorjde, and sepaiatjon of mixtures produced. These diarylsuiphides are useful as additives in lubricating oils of the extreme pressure type
Description
represented by commercial compounds such as and di(Stnonyl2.. hydroxypheny1) suiphide, have been synthesised traditionally from the petrochemical intermediates 4- t-octylphenol and 4-t-nonylphenol by reaction with sulphur dichloride. They are and have been employed as magnesium salts and then formulated for use as additives in lubricating oils of the extreme pressure type which function by chemical and physical interaction at the interface between metal surfaces.
In the long term, fossil fuel resources from which the intermediates propylene and isobutylene are obtained for the synthesis of t-octyl and tnonylphenol, are in diminishing supply and increasing cost, and it has been of interest to examine obtaining related structures from alternative natural renewable supplies. The phenolic lipid resource Anacardium occidentale, the cashew, and its relative Anacardium giganteum, more particularly the former, are available in many parts of the equatorial world 1,2,3 The cashew tree is a source of the cashew nut, produced to the extent of more than 0.5 x 106 tonnes and from the shell the commercially useful cashew nutshell liquid (CNSL) has been manufijcured for many years. In this a roasting process of raw nuts is used in which decarboxylation of the principal natural component in the shell, anacardic acid (1), occurs to give mainly cardanol (2), by bursting of the shell and the accompanying release of the highly prized edible kernel.
The liquid product of the roasting, technical CNSL, is rich in cardanol, (2), (70%), cardol, (3)(15-20%) and minor amounts of other components (4) together with Polymeric material and each of the phenols consists of a mixture of saturated, 8(Z)- monoene,8(Z),l l(Z)-djene and 8(Z),1 l(Z),14-trjene constituents as shown in Fig.1, Anacardium giganteum, wbich is botanically related to the cashew is different in composition and structurally contains a saturated C11 side chain instead of a C15,with no unsaturated constituents.
For many purposes the mixture, technical CNSL is used commercially, notably in the production of friction dusts, but in certain chemical applications such as in the present invention, cardanol is required in purer and in the saturated form, as 3- pentadecyiphenol.
Cardanol has been obtained from technical CNSL by phase distribution, base addition and distillation and a selective hydroxymethylatjon6 and a Mannich base procedure An advantage of procedures involving final vacuum distillation is the removal of cardanol dinier.
In the present invention cardanol (2) was obtained by such described methods, for example, base addition and distillation, and then converted to the saturated form (2, n = 0) by catalytic hydrogenation in ethanolic solution in the presence of 10% palladium-carbon catalyst or by chemical reduction with diimide 8 Anagigantic acid was obtained from Brazil and catalyticaly decarboxylated by heating with 10% calcium hydroxide to give 3-undecylphenol.
In this invention, thiobisphenols were synthesised by the reaction of saturated cardanol, (3-pentadecylphenoj 5, n =15, m = 0), anagigantol (3undecylphenol, 5, n =11, m = 0), cardanol monoene (5, n = 15, m 2), cardanol, 5, n 15, m O,2, 4,6).wjth sulphur dichloricle.
The reactions proceeded by way of the non-isolated, isomeric intermediate sulphenyl chlorides (6) and (7), to give the products, the minor 2,2'thiobisphenol (8) and the major 4,4'-thiobisphenol (9) with formation of small amounts of the isomeric 2,4' compound (10) as illustrated in Fig. 2. Classical researches indicate 4-substitution to be predominant.
For the technical evaluation of thiobis phenols synthesised from alkyiphenols derived from natural sources, standard commercial petrochemical products based on 4-t-octyl and 4-t-nonylpheno], namely, di-[2-hydroxy-5...(1,j3,3-tetramethylbutyl) phenyl]sulphjde (11) and (12) were used.
OHOH
C8H17 9 19 (11) (12) A minor aspect in favour of products synthesised from naturally-based phenols compared those petrochemicallyderjved is that the sidechajns in the former, as judged by the results from polyethoxylates of the two types, are more biodegradable.
Some typical thiobisphenols synthesised from naturally-derived alkylphenols are now described.
Synthesis of Thiobisphenoj from Natural Resource Alkyiphenols
Example 1
Synthesis of Thiobis Phenols from 3-Pentadecylpheno/ 44'-Thiobis-(3-pentadecylpheno1), (9, n =15, m = 0) and 22'-thiobis-(5-pentadecylpheno1) di-(2-hydroxy-4pentadecylphenyl)..sulphide (8, n = 15, m = 0). Very small amounts of the 2,4'isomer (10) were formed and some residual suiphenyl chlorides (6) and (7) were detected..
A variety of experiments were carried out with saturated cardanol (2 mol) and sulphur dichloride (imol), at 0 C with different solvents, including, benzene, light petroleum, n-hexane, chloroform, acetonitrjle and with different catalysts, anhydrous aluminium chloride, iron, and triphenylphosphjne oxide. A typical experiment with benzene as solvent in the absence of a catalyst is described. Sulphur dichioride was purified by distillation from phosphorus trichioride and obtained with bp 58-61 C.
To 3-pentadecylphenol (lO.Og, O.O33mol) in dry benzene (100cm3) stirred and cooled in an ice-bath, sulphur dichloride (I.69g, O.016mo1) in dry benzene (20cm3) was added dropwise under nitrogen over lh and the mixture then stirred for 6h (with TLC monitoring, chloroform-ethyl acetate, 95:5) and then left for 1 6h to warm to ambient temperature. The mixture, diluted with light petroleum (40-60 C) was partially concentrated, washed with water (2x50cm3), dried (sodium sulphate) and a sample separated by prep TLC (CHC13-EtOAc, 98:2) which showed two main bandsand some unchanged 3-pentadecylphenol. The whole mixture was then separated by flash chromatography, by elution with CHC13,to give fractions 1-20, (CHCI3-EtOAc, 98:2), fractions 2 1-26, (CHCI3-EtOAc, 95:5), fractions 2770. Fractions 4-8 contained the high Rf component, the 2,2'-isomer, l.48g (14.1%), mp 53-55 C; m/z, M', found: 638.5090. Required for C42H7002s, 638.5092; and fractions 46-62 gave the low Rf component, the 4,4'-isomer, 3.92g,crystafljsatjon of which (light petroleum, 60-80 C) gave 2.94g (27.9%), mp 77-79 C; Found: C, 78.76; Ii, 10.95; S, 4.95. Required for C42H7002S, C, 78.93; H, 11.04; S, 5.02%. From certain fractions 3-pentadecylphenol was recovered.
Example 2
To avoid a chromatographic separation, the mixed product isolated from the reaction mixture (monitored by TLC) of saturated cardanol with sulphur dichioride, was used in experimental evaluations.
To 3-pentadecylphenol (12.Og, O.0395mo1) in chloroform (50cm3), cooled in an ice- bath sulphur dichlorjde (2.24g, O.0217mo1) was added dropwise over 1 hour under a nitrogen stream which removed evolved hydrogen chloride. The mixture was then allowed to warm to ambient temperature over 6hours.and concentrated to constant weight by rotary evaporation in vacuo to give an oil (1 3.0g).
Example 3
In a polar solvent the ratio of the yield of the 4,4' to the 2,2' isomer was increased as shown in the following experiment.
3-Pentadecylphenol (2.Og, 6.58 x lO3mol) in acetontrile (20cm3? cooled in an ice-bath sulphur dichloride (O.37g, 3.62 x 103mo1) in acetonitrile (15cm) was added dropwise under nitrogen over 25min. The mixture was allowed to warm to ambient temperature for l6hours, diluted with diethyl ether, concentrated in vacuo and the residue column chromatographed on silica gel (hOg) by elution with chloroform, chloroform-ethyl acetate (95:5) and chloroformethyl acetate (90:10) to give recovered 3pentadecyiphenol (O.86g), the 2,2'-thjobjs isomer (0.1 5g, 7.15%) and the 4,4'isomer (O.58g, 27.3%, 48% on 3-pentadecylphenol used) in an isomer ratio, 4,4' to 2,2',of 3.8:1.
Example 4
In a polar solvent with a catalyst, the ratio (4,4'12,2') of isomers was further enhanced. 3-Pentadecylphenol (2.Og, 6.58 x 103mo1) in acetonitrile (20cm3) containing iron powder (O.02g, 10%) was stirred and cooled in an ice-bath and treated with sulphur dichioride O.37g, 3.62 x lO3mol) in acetonitrjje (15cm3) dropwise under nitrogen over 25 miii. The mixture was allowed to warm to ambient temperature over I 6hours and was concentrated in vacuo. The residue was diluted with water, extracted with diethyl ether, and the ether layer separated and dried with sodium sulphate.
Concentratratjon in vacuo gave a dark brown oil, (2.Og) of which was separated by flash chromatography with chloroform, followed by chloroformethyl acetate to give the 2,2'-isomer (O.O9g, 4.3%), unreacted 3-pentadecylphenol (1. l4g), and the 4,4'- isomer (O.48g, 22.9%, 53% on 3-pentadecylphenol used), representing an isomer ratio, 4,4'/2,2' of 5.5. Some intermediate fractions contained small amounts of all the above components and traces of suiphenyl choride material.
Example 5
3-Undecyiphenol was converted to a mixture of 4.4'- and 2.2'thiobisphenola, namely (9, n 11, m = 0), di-( 4-hydroxy2undecy1phefly1).suJphide and (8, n 11, m 0), respectively.
3-Undecylphenol (S.35g, O.2l6mol) in chloroform (50cm3) was cooled and stirred in an ice-water bath and treated dropwise with sulphur dichloride (1.23g, O.Ol9mol) in chloroform (30cm3) over l2Omin. under a nitrogen stream to remove hydrogen chloride. The mixture was allowed to warm to ambient temperature and then separated by flash chromatography on silica gel (200g) with chloroform (600cm3) to give fractions 1-5, the 2,2'thiobisphenol (O.80g, 14.1%) and chioroform-ethylacetate (95:5), to give fractions 30 to the end, containing the 4.4'- thiobisphenol, (2,25g, 39.6%).
Example 6
Cardanol mono ene (2, n = 2) prepared by catalytic reduction of cardanol (2) with a nickel catalyst and believed to comprise the 8(Z)- and 11(Z)isomers was reacted with sulphur dichioride. Cardanol (2), (4.0g) in ethanol (10cm3) containing W6 type Raney nickel (O.40g) was hydrogenated at ambient tmperature and pressure to remove the triene and diene constituents (argentatjon TLC monitoring). The mixture was released to the atmosphere under nitrogen, the catalyst removed by filtration and the filtrate concentrated to give the monoene.
To cardanol monoene (S.94g, O.Ol97mol) in chloroform (15cm3) cooled in an ice-bath sulphur dichloride (1.11 g, 0.01 O8mol) in chloroform (15cm3) was added dropwise under nitrogen over 1 hour. After warming to ambient temperature the reaction mixture was concentrated in vacuo to give a yellow oil (6.78g). The product from chromatographic analysis was a mixture of some starting material, the 4, 4'- thiobisphenol, and the 2,2'-isomer, in which some of the hydrogen chloride produced in the reaction had added to the double bond.of the cardanol monoene.
Cardanol (2) (14g, O.O45mol) in choroform (20cm3) cooled in an ice-bath was treated dropwise with sulphur dichioride (2.63g, O.O255mo1) in chloroform (20cm3) under nitrogen over SOmin.and the mixture left to stir and warm to ambient temperature.
TLC indicated a composition typical of two isomeric thiobisphenols, but appearded likely to contain products from interaction at the side chain as well as the ring The mixture was concentrated by evaoration in vacuo.
Reference compounds (11) and (12) To 4-(l,l',3,3'-tetramethylbuty1)phno1 (2O.6g, O.lOmoI) in n-hexane (75cm3) stirred and cooled in an ice-bath, sulphur dichioride (S.67g, 0.OSSmol) in n-hexane (25cm3) was added dropwise under nitrogen over 1.5 hours. The mixture was left for 1 6hours to warm to ambient temperature and the white solid which separated was filtered and washed with n-hexane (15cm3) to afford after drying, the product, di-[5- (1, 1 3,3'- tetramethylbutyl)2hytho,phenylJsulphide (11), (9.7lg, 43.9%), mp 132- 133 C (lit.'0 132-134 C).
By the reaction of the commercial mixture, t-nonylphenol (lOg, O.O485mol) in an ice- bath, in chloroform (30cm3) with sulphur dichioride (2.474g, O.025mo1) in chloroform (15cm3), added dropwise under nitrogen over 1 hour, followed by warming to ambient temperature over 3 hours, di-(StnonyJ-2...hyclroxyphenyl)... sulPhide was obtained after In evaluations as formulated, overbased', additives in lubricating oils, the 4,4'- thiobisphenol (9, n = 15, m = 0) from 3-pentadecylphenol, showed a comparable performance to formulated commercial additives such (11) and (12). For practical purposes, mixed products containing a major proportion of the 4,4'isomer and some 2,2'-isomer were useful.
References I. J G Ohier, Cashew, The Royal Tropical Institute, Amsterdam, The Netherlands, 1979.
2. 0 Arango, I Pischedda and R Zobolj, The World Cashew Economy, L'inchiostroblu, Nomisma, Bologna, Italy, 1987.
3. J H P Tyman, Synthetic and Natural Phenols, Elsevier Science, Amsterdam, The Netherlands, 1996, Ch. 13.
4. J H P Tyman, I E Bruce and P Payne, Natural Product Letters, 1992, 1, 117-120.
5. MPateI,JHPTynna11dAM Ja,UKPatentAj 8100208 (Jan6 1981).
6. J HP Tyman and S K Mehet, Chem. and Phys. of Lipids, 2003, 126, 177199.
7. J H P Tyman,.UK Patent Appln. GB 2152925A (Oct 24 1983).
8. S K Lam and J HP Tynian, JChem. Soc., Perldn Trans 1, 1982, 1942-1952.
9. J HP Tyman and I E Bruce, JSurfactants and Detergents, 2004, 7, 169173.
10. A M Nicholson and B Zarensky, USP 2971968, (Feb. 14, 1961). / ct:)
Claims (4)
- Claims 1 A process for the synthesis ofthiobisphenols by the reaction ofsulphur dichioride with 3-pentadecylphenol, from cardanol, derived from cashew nutshell liquid, a renewable phenolic resource obtained from Anacardium occidentale.
- 2 A process for the synthesis ofthiobisphenols by the reaction of sulphur dichioride with 3-undecylphenol obtained from Anacardium giganreum, a renewable phenoljc resource.
- 3 A process for the synthesis of thiobisphenojs by the reaction of sulphur dichloride with phenols from the said phenols in Claims I and 2 in the presence of a catalyst.
- 4 The reaction of related 3-alkylphenols derived by transformation from natural phenolic resources with sulphur dichlorjde to produce thiobisphenols.The use ofthiobisphenols produced as in Claims 1, 2, 3 and 4 as additives in lubricating oils.4 The reaction of similar 3-alkylphenojs from related natural resources, with sulphur dichioride to produce thiobisphenols The use of other 2- and 4-alkylphenols from renewable resources for synthesising thiobisphenols in a similar way.6 The use of thiobisphenols produced as in Claims 1, 2, 3 and 4 as additives in lubricating oils.Amendments to the claims have been filed as follows Claims 1 A process for the synthesis of thiobisphenols by the reaction of sulphur dichloride with 3-pentadecylphenol, from cardanol, derived from cashew nutshell liquid, a renewable phenolic resource obtained from Anacardium occidentale.2 A process for the synthesis of thiobisphenols by the reaction of sulphur dichioride with 3-undecylphenol obtained from Anacardjum giganteum, a renewable phenoljc resource.3 A process for the synthesis of thiobisphenols by the reaction of sulphur dichioride with phenols from the said phenols in Claims 1 and 2 in the presence of a catalyst.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2181119A (en) * | 1939-11-28 | Derivatives of a phenol obtained | ||
| GB616881A (en) * | 1946-05-27 | 1949-01-28 | Francis Hayward Ayden | Improvements in or relating to lubricating compositions |
| GB664169A (en) * | 1948-01-27 | 1952-01-02 | British Resin Prod Ltd | Improvements in or relating to purified cashew nut shell liquid and derivatives thereof |
| GB2120656A (en) * | 1982-05-26 | 1983-12-07 | Koppers Co Inc | Preparation of thio-bis-phenols |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT1264075B1 (en) * | 1993-09-09 | 1996-09-10 | Consiglio Nazionale Ricerche | Process for the production of sulphurated antioxidants from derivatives of cashew nut shell oil |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2181119A (en) * | 1939-11-28 | Derivatives of a phenol obtained | ||
| GB616881A (en) * | 1946-05-27 | 1949-01-28 | Francis Hayward Ayden | Improvements in or relating to lubricating compositions |
| GB664169A (en) * | 1948-01-27 | 1952-01-02 | British Resin Prod Ltd | Improvements in or relating to purified cashew nut shell liquid and derivatives thereof |
| GB2120656A (en) * | 1982-05-26 | 1983-12-07 | Koppers Co Inc | Preparation of thio-bis-phenols |
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