US2382775A - Dithiophosphoric acids and salts thereof - Google Patents
Dithiophosphoric acids and salts thereof Download PDFInfo
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- US2382775A US2382775A US447274A US44727442A US2382775A US 2382775 A US2382775 A US 2382775A US 447274 A US447274 A US 447274A US 44727442 A US44727442 A US 44727442A US 2382775 A US2382775 A US 2382775A
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- 150000003839 salts Chemical class 0.000 title description 7
- 239000002253 acid Substances 0.000 title description 6
- 150000007513 acids Chemical class 0.000 title description 3
- -1 hydrogen radicals Chemical class 0.000 description 26
- 150000001875 compounds Chemical class 0.000 description 10
- 125000004432 carbon atom Chemical group C* 0.000 description 9
- 125000000217 alkyl group Chemical group 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 5
- 150000003254 radicals Chemical class 0.000 description 5
- 229910052788 barium Inorganic materials 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 239000010687 lubricating oil Substances 0.000 description 4
- 229910052751 metal Chemical class 0.000 description 4
- 239000002184 metal Chemical class 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 125000000753 cycloalkyl group Chemical group 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- 159000000009 barium salts Chemical class 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- NAGJZTKCGNOGPW-UHFFFAOYSA-N dithiophosphoric acid Chemical compound OP(O)(S)=S NAGJZTKCGNOGPW-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- ZGTYIANLCXIHFG-UHFFFAOYSA-N 1-(2,4-ditert-butylphenoxy)ethanol Chemical compound CC(O)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C ZGTYIANLCXIHFG-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical class [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- OCBFFGCSTGGPSQ-UHFFFAOYSA-N [CH2]CC Chemical group [CH2]CC OCBFFGCSTGGPSQ-UHFFFAOYSA-N 0.000 description 1
- PQGAHNJECSVDEI-UHFFFAOYSA-N [CH2]CCCCC Chemical compound [CH2]CCCCC PQGAHNJECSVDEI-UHFFFAOYSA-N 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- QUPDWYMUPZLYJZ-UHFFFAOYSA-N ethyl Chemical compound C[CH2] QUPDWYMUPZLYJZ-UHFFFAOYSA-N 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 229960004592 isopropanol Drugs 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N isopropyl alcohol Natural products CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002730 mercury Chemical class 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000001421 myristyl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 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
- 125000005359 phenoxyalkyl group Chemical group 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- RPACBEVZENYWOL-XFULWGLBSA-M sodium;(2r)-2-[6-(4-chlorophenoxy)hexyl]oxirane-2-carboxylate Chemical group [Na+].C=1C=C(Cl)C=CC=1OCCCCCC[C@]1(C(=O)[O-])CO1 RPACBEVZENYWOL-XFULWGLBSA-M 0.000 description 1
- 125000004079 stearyl 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])C([H])([H])C([H])([H])C([H])([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
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
Classifications
-
- 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
- C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
- C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
- C10M137/04—Phosphate esters
- C10M137/10—Thio derivatives
- C10M137/105—Thio derivatives not containing metal
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/16—Esters of thiophosphoric acids or thiophosphorous acids
- C07F9/165—Esters of thiophosphoric acids
- C07F9/1651—Esters of thiophosphoric acids with hydroxyalkyl compounds with further substituents on alkyl
-
- 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
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
- C10M2223/047—Thioderivatives not containing metallic elements
-
- 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
- C10N2010/00—Metal present as such or in compounds
- C10N2010/02—Groups 1 or 11
-
- 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
- C10N2010/00—Metal present as such or in compounds
- C10N2010/04—Groups 2 or 12
-
- 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
- C10N2010/00—Metal present as such or in compounds
- C10N2010/06—Groups 3 or 13
-
- 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
- C10N2010/00—Metal present as such or in compounds
- C10N2010/08—Groups 4 or 14
-
- 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
- C10N2010/00—Metal present as such or in compounds
- C10N2010/14—Group 7
-
- 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
- C10N2010/00—Metal present as such or in compounds
- C10N2010/16—Groups 8, 9, or 10
Definitions
- R1 and R2 are members of the group consisting of alkyl, cycloalkyl and hydrogen radicals at least one being a member of the group consisting of alkyl and cycioalkyl radicals
- R3 is an alkylene radical containing 2-4 carbon atoms inclusive
- X is a member of th group consisting of hydrogen and metal salt-forming radicals
- n is the valence of X.
- Our new compounds may be prepared by adding approximately 4 mols of an alkyl or cycloalkyl substituted phenoxyalkylol with one mol of P285 at temperatures between 90-110 C. until most of the P285 has dissolved and the evolution of H28 has subsided.
- the crude product may be decanted from unreacted P285 and employed as such for certain purposes or it may be neutralized with a suitable salt-forming base as will hereinafter be described.
- R1 and R2 are members of the group consisting of hydrogen, alkyl and cycloalkyl radicals of from about 1-20 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, n-amyl, tertiary amyl, ethylhexyl, cyclopentyl, cyclohexyl, methylcyclohexyl, dimethylcyclohexyl and the ethyl, propyl, butyl and amyi 'mono-, diand tri-substituted cyclohexyl radicals.
- Either R1 or R2 or both R1 and R2 may be alkyl or cycloalkyl radicals as indicated.
- both R1 and Re be alkyl radicals having a total number of carbon atoms equal to at least 8. More specifically, when R1 is a propyl radical R2 should be an alkyl radical at least as long as an amyl radical, R1 and R2 may both be butyl radicals, R1 may be a hexyl radical and R2 an ethyl radical.
- R2 should be a radical of at least 8 carbon atoms such as octyl, dodecyl, tetradecyl, octadecyl or the like.
- Specific compounds of this group include 2,4-ditertiarybutylphenoxy ethanol, 4-octylphenoxy ethanol, 4-amyl-2-isopropylphenoxy ethanol, 4-octylphenoxy propanol, 2,4- diamylphenoxy iso-propanol, 2,4-diethylhexylphenoxy ethanol and others of a similar character.
- Metal salts of the bis(alkyl or aryl substituted phenoxy alkyl) dithiophosphoric acids may be prepared by simple neutralization of the acid with a suitable salt-forming base or by doubledecomposition.
- suitable salt-forming base or by doubledecomposition.
- salt-forming radicals include thoseof Ni, Al, Pb, Hg, Cd, Sn,
- Zn, Mg, Na, K, N'H4, Ca, Sr, Ba and others which may be introduced by neutralization of the acid with a corresponding oxide, hydroxide or carbonate and in some cases sulfide.
- Some of these salts may be more easily prepared by doubledecomposition of the Na salt of the dithiophosphoric acid with a desired metal salt, for example ZnClz etc. 7
- Example 100 parts by weight of 2,4-diamylphenoxy ethanol was stirred and heated for 3.5 hours at 95-105 C. with 22 parts by weight of finely ground P285. At the end of this time practically all of the P285 had dissolved and the evolution of the H2S subsided
- the barium salt of the above product was prepared by dissolving 90 parts by weight thereof in 30 parts by weight of tolueneand 20 parts by weight of ethanol. 12 parts by weight of finely powdered barium oxide was added and the mixture was warmed at 40-50 C. for 30 minutes at the end of which time the dithiophosphoric acid was neutralized. After filtration of traces of inorganic barium salts the solvent was evaporated, the last of the solvent being removed under reduced pressure. Barium bis(2,4-dia.mylphenoxyethyl) dithiophosphate remained as a yellow liquid that was practically insoluble in water but easily soluble in hydrocarbon lubricating oils.
- R1 and R are alkyl radicals having a. combined number of carbon atoms of at least 8
- R3 is an alkylene radical containing 2 to 4 carbon atoms inclusive
- X is a metal selected from the group consisting of calcium, barium, strontium, magnesium, zinc, mercury, cadmium and tin.
- R1 and R2 are alkyi radicals having a combined number of carbon atoms of at least 8
- R3 is an alkylene radical containing 24 carbon atoms inclusive
- X is an alkaline earth metal.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
Description
Patented Aug. 14, 1945 UNITED STATES PATENT OFFICE I DITHIOPHOSPHORIC ACIDS AND SALTS THEREOF I Elmer William Cook, New York, N. Y., and William David Thomas, Jr., Stamford, Conn., as-
slgnors to American Cyanamid Company, New York, N. Y., a corporation of Maine No Drawing. Application June is, 1942,
Serial No. 447,274 1 4 Claims.
5 m0 1 f R1 in which R1 and R2 are members of the group consisting of alkyl, cycloalkyl and hydrogen radicals at least one being a member of the group consisting of alkyl and cycioalkyl radicals, R3 is an alkylene radical containing 2-4 carbon atoms inclusive, X is a member of th group consisting of hydrogen and metal salt-forming radicals, and n is the valence of X.
Many of the compounds of the above class have both detergent and corrosion inhibiting properties and when dissolved in hydrocarbon lubricating oils are extremely valuable in the prevention of bearing corrosion, sludgeand varnish for nation, ring sticking and other undesirable conditions which develop when ordinary lubrieating oil are subjected to heavy duty service. Being water insoluble and polar in character they are valuable in the preparation of slushing oils. Because of their sulfur and phosphorus content they may be advantageously added to hypoid gear greases and other extreme pressure lubricants. Some of the compounds of the groups are also useful in the flotation of ores and ome of their salts, particularly the lead and mercury salts, may be employed in insecticides and fungicides.
Our new compounds may be prepared by adding approximately 4 mols of an alkyl or cycloalkyl substituted phenoxyalkylol with one mol of P285 at temperatures between 90-110 C. until most of the P285 has dissolved and the evolution of H28 has subsided. The crude product may be decanted from unreacted P285 and employed as such for certain purposes or it may be neutralized with a suitable salt-forming base as will hereinafter be described.
substituted phenoxyalkylols having the general formula v (|)R3OH in which Re is an alkylene radical of 2-4 carbon atoms such as CH2CH2,
C HaCHr- CH2CH2CH2, etc., and R1 and R2 are members of the group consisting of hydrogen, alkyl and cycloalkyl radicals of from about 1-20 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, n-amyl, tertiary amyl, ethylhexyl, cyclopentyl, cyclohexyl, methylcyclohexyl, dimethylcyclohexyl and the ethyl, propyl, butyl and amyi 'mono-, diand tri-substituted cyclohexyl radicals. Either R1 or R2 or both R1 and R2 may be alkyl or cycloalkyl radicals as indicated.
Since the compounds of the present invention have been found to be of particular'value in lubricating oil as corrosion inhibitors and deter- As will appear from the general formula given gents it is preferred that they be easily soluble in ordinary hydrocarbon lubricating oils. In order that the compounds of the present invention may possess the requisite 'oil solubility it is therefore desirable that both R1 and Re be alkyl radicals having a total number of carbon atoms equal to at least 8. More specifically, when R1 is a propyl radical R2 should be an alkyl radical at least as long as an amyl radical, R1 and R2 may both be butyl radicals, R1 may be a hexyl radical and R2 an ethyl radical. When R1 is hydrogen then R2 should be a radical of at least 8 carbon atoms such as octyl, dodecyl, tetradecyl, octadecyl or the like. Specific compounds of this group include 2,4-ditertiarybutylphenoxy ethanol, 4-octylphenoxy ethanol, 4-amyl-2-isopropylphenoxy ethanol, 4-octylphenoxy propanol, 2,4- diamylphenoxy iso-propanol, 2,4-diethylhexylphenoxy ethanol and others of a similar character.
Metal salts of the bis(alkyl or aryl substituted phenoxy alkyl) dithiophosphoric acids may be prepared by simple neutralization of the acid with a suitable salt-forming base or by doubledecomposition. A wide variety of salt-forming radicals include thoseof Ni, Al, Pb, Hg, Cd, Sn,
Zn, Mg, Na, K, N'H4, Ca, Sr, Ba and others which may be introduced by neutralization of the acid with a corresponding oxide, hydroxide or carbonate and in some cases sulfide. Some of these salts may be more easily prepared by doubledecomposition of the Na salt of the dithiophosphoric acid with a desired metal salt, for example ZnClz etc. 7
The preparation of our new compounds will now be described in greater detail by means of the following example in which the preparation of bis(2,4-diamylphenoxyethyl) dithiophosphoric acid and the Ba salt thereof is described. It will be understood that our invention is not limited to the preparation of this particular compound since it is given primarily for purposes of illustration and our invention is to be construed only by the scope of the appended claims.
Example 100 parts by weight of 2,4-diamylphenoxy ethanol was stirred and heated for 3.5 hours at 95-105 C. with 22 parts by weight of finely ground P285. At the end of this time practically all of the P285 had dissolved and the evolution of the H2S subsided The product, crude bis(2,4-diamylphenoxyethyl) dithiophosphoric acid, a light brown liquid, was recovered by decantation from the small amount of unreacted Pass.
The barium salt of the above product was prepared by dissolving 90 parts by weight thereof in 30 parts by weight of tolueneand 20 parts by weight of ethanol. 12 parts by weight of finely powdered barium oxide was added and the mixture was warmed at 40-50 C. for 30 minutes at the end of which time the dithiophosphoric acid was neutralized. After filtration of traces of inorganic barium salts the solvent was evaporated, the last of the solvent being removed under reduced pressure. Barium bis(2,4-dia.mylphenoxyethyl) dithiophosphate remained as a yellow liquid that was practically insoluble in water but easily soluble in hydrocarbon lubricating oils.
Since other alkyl and cycloalkyl substituted phenoxyalkylols may be reacted with P285 in the same way using similar proportions of materials and reaction conditions further description of the preparation of these products is not thought necessary.
We claim:
1. Chemical compounds having the formula RHQ Q41, x Ra R:
in which R1 and R: are alkyl radicals having a. combined number of carbon atoms of at least 8, R3 is an alkylene radical containing 2 to 4 carbon atoms inclusive, and X is a metal selected from the group consisting of calcium, barium, strontium, magnesium, zinc, mercury, cadmium and tin.
2. Chemical compounds having the general formula in which R1 and R2 are alkyi radicals having a combined number of carbon atoms of at least 8, R3 is an alkylene radical containing 24 carbon atoms inclusive, and X is an alkaline earth metal.
3. Barium bis(2,4-diamyl phenoxyethyl) diithiophosphoric acid.
4. Barium bis(2,4-dibutyl phenoxyethyl) dithiophosphoric acid.
ELMER WILLIAM COOK. WILLIAM DAVID THOMAS, JR.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US447274A US2382775A (en) | 1942-06-16 | 1942-06-16 | Dithiophosphoric acids and salts thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US447274A US2382775A (en) | 1942-06-16 | 1942-06-16 | Dithiophosphoric acids and salts thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2382775A true US2382775A (en) | 1945-08-14 |
Family
ID=23775692
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US447274A Expired - Lifetime US2382775A (en) | 1942-06-16 | 1942-06-16 | Dithiophosphoric acids and salts thereof |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2382775A (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2516119A (en) * | 1945-08-09 | 1950-07-25 | Continental Oil Co | Metal, phosphorus, and sulfur-containing organic compounds |
| US2579037A (en) * | 1947-12-09 | 1951-12-18 | Wakefield & Co Ltd C C | Lubricating composition |
| US2737492A (en) * | 1952-03-26 | 1956-03-06 | American Cyanamid Co | Lubricating oil compositions |
| US2900377A (en) * | 1956-06-26 | 1959-08-18 | Standard Oil Co | Phosphorus sulfide derivatives of hexachlorocyclopentadienepolyolefin adducts |
| US2927080A (en) * | 1956-08-06 | 1960-03-01 | Exxon Research Engineering Co | Corrosion inhibitor |
| US2978412A (en) * | 1956-09-25 | 1961-04-04 | Exxon Research Engineering Co | Copolymers of phosphorus sulfides and unsaturated organic esters |
| US3002014A (en) * | 1958-07-30 | 1961-09-26 | Monsanto Chemicals | S-amine phosphorothioates |
| US3068259A (en) * | 1959-02-12 | 1962-12-11 | Gulf Research Development Co | Molybdenum and tungsten halides and sulfides of organic substituted dithiophosphoricacids |
| US3135694A (en) * | 1953-08-07 | 1964-06-02 | American Cyanamid Co | Alkoxymethyl esters of 2-mercapto 2-thiono 1, 3, 2-dioxaphosphorinane acids |
| US3243482A (en) * | 1962-01-10 | 1966-03-29 | Gen Aniline & Film Corp | Surface-active thiophosphoric acid esters of polyglycol ethers |
| US4071545A (en) * | 1975-10-02 | 1978-01-31 | Stauffer Chemical Company | Preparation of S-tricyclohexyltin-O,O-diisopropyl dithiophosphate |
| US4259192A (en) * | 1979-04-02 | 1981-03-31 | Chevron Research Company | Lubricating oil compositions containing polyether dithiophosphates |
-
1942
- 1942-06-16 US US447274A patent/US2382775A/en not_active Expired - Lifetime
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2516119A (en) * | 1945-08-09 | 1950-07-25 | Continental Oil Co | Metal, phosphorus, and sulfur-containing organic compounds |
| US2579037A (en) * | 1947-12-09 | 1951-12-18 | Wakefield & Co Ltd C C | Lubricating composition |
| US2737492A (en) * | 1952-03-26 | 1956-03-06 | American Cyanamid Co | Lubricating oil compositions |
| US3135694A (en) * | 1953-08-07 | 1964-06-02 | American Cyanamid Co | Alkoxymethyl esters of 2-mercapto 2-thiono 1, 3, 2-dioxaphosphorinane acids |
| US2900377A (en) * | 1956-06-26 | 1959-08-18 | Standard Oil Co | Phosphorus sulfide derivatives of hexachlorocyclopentadienepolyolefin adducts |
| US2927080A (en) * | 1956-08-06 | 1960-03-01 | Exxon Research Engineering Co | Corrosion inhibitor |
| US2978412A (en) * | 1956-09-25 | 1961-04-04 | Exxon Research Engineering Co | Copolymers of phosphorus sulfides and unsaturated organic esters |
| US3002014A (en) * | 1958-07-30 | 1961-09-26 | Monsanto Chemicals | S-amine phosphorothioates |
| US3068259A (en) * | 1959-02-12 | 1962-12-11 | Gulf Research Development Co | Molybdenum and tungsten halides and sulfides of organic substituted dithiophosphoricacids |
| US3243482A (en) * | 1962-01-10 | 1966-03-29 | Gen Aniline & Film Corp | Surface-active thiophosphoric acid esters of polyglycol ethers |
| US4071545A (en) * | 1975-10-02 | 1978-01-31 | Stauffer Chemical Company | Preparation of S-tricyclohexyltin-O,O-diisopropyl dithiophosphate |
| US4259192A (en) * | 1979-04-02 | 1981-03-31 | Chevron Research Company | Lubricating oil compositions containing polyether dithiophosphates |
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