US2197462A - Process and product relating to heteropolar compounds - Google Patents
Process and product relating to heteropolar compounds Download PDFInfo
- Publication number
- US2197462A US2197462A US182005A US18200537A US2197462A US 2197462 A US2197462 A US 2197462A US 182005 A US182005 A US 182005A US 18200537 A US18200537 A US 18200537A US 2197462 A US2197462 A US 2197462A
- Authority
- US
- United States
- Prior art keywords
- ketone
- acid
- unsaturated ketone
- beta
- unsaturated
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 150000001875 compounds Chemical class 0.000 title description 43
- 238000000034 method Methods 0.000 title description 26
- 230000008569 process Effects 0.000 title description 15
- 150000002576 ketones Chemical class 0.000 description 95
- 150000002148 esters Chemical class 0.000 description 31
- 239000002253 acid Substances 0.000 description 29
- 229910052698 phosphorus Inorganic materials 0.000 description 22
- 239000003795 chemical substances by application Substances 0.000 description 18
- -1 flotation Substances 0.000 description 17
- 150000003333 secondary alcohols Chemical class 0.000 description 17
- 239000011574 phosphorus Substances 0.000 description 16
- 239000000047 product Substances 0.000 description 15
- 229920006395 saturated elastomer Polymers 0.000 description 15
- 125000001931 aliphatic group Chemical group 0.000 description 14
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 13
- 239000003054 catalyst Substances 0.000 description 13
- 238000005984 hydrogenation reaction Methods 0.000 description 13
- 230000008707 rearrangement Effects 0.000 description 13
- 229910052799 carbon Inorganic materials 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 10
- 150000001721 carbon Chemical group 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 150000003254 radicals Chemical class 0.000 description 9
- 238000009835 boiling Methods 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- 230000007935 neutral effect Effects 0.000 description 7
- 125000004430 oxygen atom Chemical group O* 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- 239000000314 lubricant Substances 0.000 description 6
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 description 6
- 125000004437 phosphorous atom Chemical group 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 150000007513 acids Chemical class 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 238000005194 fractionation Methods 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- RYYWUUFWQRZTIU-UHFFFAOYSA-N Thiophosphoric acid Chemical compound OP(O)(S)=O RYYWUUFWQRZTIU-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 239000007859 condensation product Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000000539 dimer Substances 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 238000009736 wetting Methods 0.000 description 3
- ZRKMQKLGEQPLNS-UHFFFAOYSA-N 1-Pentanethiol Chemical compound CCCCCS ZRKMQKLGEQPLNS-UHFFFAOYSA-N 0.000 description 2
- ZIXLDMFVRPABBX-UHFFFAOYSA-N 2-methylcyclopentan-1-one Chemical compound CC1CCCC1=O ZIXLDMFVRPABBX-UHFFFAOYSA-N 0.000 description 2
- SYBYTAAJFKOIEJ-UHFFFAOYSA-N 3-Methylbutan-2-one Chemical compound CC(C)C(C)=O SYBYTAAJFKOIEJ-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- 230000003292 diminished effect Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- NAGJZTKCGNOGPW-UHFFFAOYSA-N dithiophosphoric acid Chemical compound OP(O)(S)=S NAGJZTKCGNOGPW-UHFFFAOYSA-N 0.000 description 2
- 238000005188 flotation Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 150000003222 pyridines Chemical class 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 2
- 230000001180 sulfating effect Effects 0.000 description 2
- 239000013638 trimer Substances 0.000 description 2
- OGNVQLDIPUXYDH-ZPKKHLQPSA-N (2R,3R,4S)-3-(2-methylpropanoylamino)-4-(4-phenyltriazol-1-yl)-2-[(1R,2R)-1,2,3-trihydroxypropyl]-3,4-dihydro-2H-pyran-6-carboxylic acid Chemical compound CC(C)C(=O)N[C@H]1[C@H]([C@H](O)[C@H](O)CO)OC(C(O)=O)=C[C@@H]1N1N=NC(C=2C=CC=CC=2)=C1 OGNVQLDIPUXYDH-ZPKKHLQPSA-N 0.000 description 1
- OZXIZRZFGJZWBF-UHFFFAOYSA-N 1,3,5-trimethyl-2-(2,4,6-trimethylphenoxy)benzene Chemical compound CC1=CC(C)=CC(C)=C1OC1=C(C)C=C(C)C=C1C OZXIZRZFGJZWBF-UHFFFAOYSA-N 0.000 description 1
- RIFKADJTWUGDOV-UHFFFAOYSA-N 1-cyclohexylethanone Chemical compound CC(=O)C1CCCCC1 RIFKADJTWUGDOV-UHFFFAOYSA-N 0.000 description 1
- COHMZOFFBRKADW-UHFFFAOYSA-N 1-cyclopentylpropan-1-one Chemical compound CCC(=O)C1CCCC1 COHMZOFFBRKADW-UHFFFAOYSA-N 0.000 description 1
- GSSXLFACIJSBOM-UHFFFAOYSA-N 2h-pyran-2-ol Chemical compound OC1OC=CC=C1 GSSXLFACIJSBOM-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 239000005997 Calcium carbide Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 150000003797 alkaloid derivatives Chemical class 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- JPUHCPXFQIXLMW-UHFFFAOYSA-N aluminium triethoxide Chemical compound CCO[Al](OCC)OCC JPUHCPXFQIXLMW-UHFFFAOYSA-N 0.000 description 1
- 150000003974 aralkylamines Chemical class 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- PTVDYARBVCBHSL-UHFFFAOYSA-N copper;hydrate Chemical compound O.[Cu] PTVDYARBVCBHSL-UHFFFAOYSA-N 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000010730 cutting oil Substances 0.000 description 1
- 125000005265 dialkylamine group Chemical group 0.000 description 1
- 125000005266 diarylamine group Chemical group 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- TVZISJTYELEYPI-UHFFFAOYSA-N hypodiphosphoric acid Chemical compound OP(O)(=O)P(O)(O)=O TVZISJTYELEYPI-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- SHOJXDKTYKFBRD-UHFFFAOYSA-N mesityl oxide Natural products CC(C)=CC(C)=O SHOJXDKTYKFBRD-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- ODZPKZBBUMBTMG-UHFFFAOYSA-N sodium amide Chemical compound [NH2-].[Na+] ODZPKZBBUMBTMG-UHFFFAOYSA-N 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- JXAZAUKOWVKTLO-UHFFFAOYSA-L sodium pyrosulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OS([O-])(=O)=O JXAZAUKOWVKTLO-UHFFFAOYSA-L 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- VKHQYTLHHOQKSC-UHFFFAOYSA-N sulfosulfamic acid Chemical class OS(=O)(=O)NS(O)(=O)=O VKHQYTLHHOQKSC-UHFFFAOYSA-N 0.000 description 1
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- CLZWAWBPWVRRGI-UHFFFAOYSA-N tert-butyl 2-[2-[2-[2-[bis[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]amino]-5-bromophenoxy]ethoxy]-4-methyl-n-[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]anilino]acetate Chemical compound CC1=CC=C(N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)C(OCCOC=2C(=CC=C(Br)C=2)N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)=C1 CLZWAWBPWVRRGI-UHFFFAOYSA-N 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 150000007970 thio esters Chemical class 0.000 description 1
- 125000005000 thioaryl group Chemical group 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- JQPMDTQDAXRDGS-UHFFFAOYSA-N triphenylalumane Chemical compound C1=CC=CC=C1[Al](C=1C=CC=CC=1)C1=CC=CC=C1 JQPMDTQDAXRDGS-UHFFFAOYSA-N 0.000 description 1
- RNSXATQSBDUWTH-UHFFFAOYSA-N undec-5-en-4-one Chemical compound CCCCCC=CC(=O)CCC RNSXATQSBDUWTH-UHFFFAOYSA-N 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 239000000080 wetting agent 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
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
- C07C29/175—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds with simultaneous reduction of an oxo group
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C35/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring
- C07C35/02—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring monocyclic
- C07C35/06—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring monocyclic containing a five-membered rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C403/00—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone
- C07C403/14—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by doubly-bound oxygen atoms
- C07C403/16—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by doubly-bound oxygen atoms not being part of —CHO groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
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- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/20—Metal working
- C10N2040/22—Metal working with essential removal of material, e.g. cutting, grinding or drilling
Definitions
- the present invention relates to a' process for the preparation of, and products constituting, a lbroad class of heteropolar (polar-nonpolar) compounds ranging'from' neutral oil-soluble compounds to acidic or basic water-soluble compounds which have the common property of exhibiting a certain duo-nature.
- This duo-nature is manifested by an affinity on the one hand for lipins and by an affinity for water or inorganic substances on the other hand, caused by the simultaneous presence of lipophile and polar or lipophobe groups in the molecule.
- the invention concerns a process for the preparation of, and products relating to heteropolar compounds in which at least one lipophile radical is predominantly of aliphatic character, and more particularly to those compounds containing an aliphatic lipophile radical or radicals of highly branched structure.
- An object of the present invention is to provide an improved method for the production of a superior class of heteropolar compounds having at least one lipophile radical, said lipophile radical having the structure hereinafter set forth.
- alpha beta unsaturated ketone a ketone containing an ethylene linkage attached to the carbonyl group.
- ketones contain a conjugated system of the structure
- beta gamma unsaturated ketone a ketone containing an ethylene linkage attached to the carbonyl group through a methylene group.
- alpha beta unsaturated ketones applicable in the present process may be designated by the general formula:
- R1 through R1 may be any member of the group consisting of hydrogen, aliphatic and .cyclo-parafiinic groups, with the provisions that C and or C be tertiary carbon at0m(s), and
- R1, R2 and R3 radicals are Hr-CH:
- R2 may be connected with R1 or Rs by one or more methylene groups to form a polymethylene ring structure, for example, containing the groupings.
- alpha beta unsaturated ketones including their optical and stereo-isomers, constitute a class of unsaturated ketones diflering in several respects from other unsaturated ketones.
- One notable characteristic of these compounds is the ease with which they may be alkylated.
- Unsaturated ketones of other structure such as mesityl oxide, ethyl nonenone gamma delta, 3-methyl-cyclohexadienyl-2, fi-acetone, etc., which are not allwlated under mild conditions are not applicable.
- Unsaturated ketones of the desired structure may be prepared by any one of several known methods, the invention being independent of the mode of formation.
- One suitable method is through the condensation of ketones followed by dehydration of 'the resulting ketols.
- the reactions involved in the synthesis are illustrated by the case of the formation of 2, 4, 8-trimethylnonene-4-one-6 from methyl isobutyl ketone.
- Am aliphatic, alicyclic orvaliphatic alicyclic ketone having a primary or secondary alpha carbon atom such as, for example, methyl ethyl ketone, methyl isopropyl ketone, methyl cyclohexyl ketone, ethyl cyclopentyl ketone, cyclohexanone, cyclopentanone, alpha methyl cyclopentanone, etc., may be employed to form the starting material of my process.
- Any suitable catalyst such as CaCz, A1203, NaOCrHa, POCls, H2804, HCl, IIBr, HI, CaO, ThOz, ZnClz, Na, aluminum halide, organo magnesium halide, sodium pyrosulfate, sodamide, triphenyl aluminum, etc., may be used to accelerate the reaction. In most cases the two reactions proceed under the same conditions to yield the desired alpha beta unsaturated ketone directly. If under mild (usually alkaline conditions) the ketol is obtained, this may be easily dehydrated by heating with a little acid. In this method of preparation all theoretically possible condensation products are formed to a certain extent, their relative quantity being determined by the ketone, catalyst, and conditions used. Thus, for example,
- Another and convenient method for preparing the desired alpha beta unsaturated ketones is through the condensation of a ketone of the above-mentioned class with an alpha substituted aldehyde. Any aldehyde having the structure Another method of producing the desired alpha beta unsaturated ketones is through the dehydration of the corresponding acyloins. This may be accomplished according to the scheme rearranges CH: CH:
- the corresponding beta gamma unsaturated ketones undergo hydrogenation under more favorable conditions and in a cleancut manner to yield the corresponding secondary alcohols in excellent yields.
- the beta gamma ketones differ further from their corresponding alpha beta ketones in showing essentially no exalted molecular refractions and having lower melting points, boiling points, refractive indices and densities.
- I therefore rearrange the alpha beta unsaturated ketone, regardless of source, to the corresponding beta gamma imsaturated ketone before effecting hydrogenation.
- the tertiary carbon atoms (0* and/or C in the above-mentioned alpha beta unsaturated ketone structure counteract to a certain extent the tendency of the unsaturated bonds to conjugate, i. e., to form static alpha beta unsaturated ketones.
- This counteracting tendency manifests itself in the formation of an equilibrium mixture at alpha beta and beta gamma unsaturated ketone in which the beta gamma ketone content may range from traces to an appreciable amount depending upon the size and character of the radicals, R1, 2, 3, and 4.
- the alpha beta unsaturated ketone or an equilibrium mixture of alpha beta and beta gamma unsaturated ketone
- the lower boiling beta gamma unsaturated ketone may be continually removed causing the rearrangement to proceed to completion.
- the rate of rearrangement is somewhat dependent upon the amount 01 catalyst present, being somewhat higher at catalyst concentration of about 3 to 5%. While the lower boiling alpha beta unsaturated ketones are conveniently rearranged at their normal boiling points, such high molecular weight unsaturated ketones as are unstable at their normal boiling points may be rearranged at a somewhat lower temperature by carrying out the rearrangement under a suitably diminished pressure.
- any desired alpha beta unsaturated ketone is usually accompanied by the formation of a small amount of other condensation products.
- these products usually consist of isomeric alpha beta unsaturated ketones and alpha beta unsaturated ketones of different molecular weight they may beqearranged to their corresponding beta gamma unsaturated ketones in the same manner and are suitable for the preparation of valuable heteropolar compounds,
- heteropolar compounds consisting of a single compound or a mixture of closely relatedisomers are in most cases far superior to any mixture of compounds, it is usually desirable to separate the various products before attaching the polar groups.
- This separation which may be neglected if desired, may be efiected at any one of three stages in the preparation, namely, previous to the rearranging, during the rearranging, or after the hydrogenation. Since in the rearrangement step the'material is subjected to a slow fractionation, the separation is most conveniently carried out during this operation, it being 'merely necessary to collect the promptly as possible. Since, however, in the maof from 1 to of an active hydrogenation catalyst such as nickel, using about 500 lbs. per square inch pressure and a temperature of about 150 C. However, other conditions including temperatures from 60 C. to about 250 C., pres-.
- Vapor phase hydrogenation although applicable in many cases, is not as practical as the liquid phase hydrogenation and therefore not preferred. Any traces of sulfur tending to poison the catalyst may be removed previous to hydrogenation by first subjecting the beta gamma unsaturated ketone to a treatment with copper hydrate, spent catalyst or some other suitable agent in the known manner.
- any,- of the common polar groups certain polar groups are more practical than others.
- the polar groups Cl, Br, --I, SH, CN and NO: are not easily attached to the present lipophile groups and moreover form heteropolar compounds of very restricted utility.
- the. unsaturated ketones contain the polar carbonyl group, and are in reality heteropolar compounds. Due to-the weakness of the polar group and the unfavorable balance of these compounds, they are, however, of practically no value as h'eteropolaragents.
- the secondary alcohols of the present'invention are likewise hateropolar compounds, since they contain the polar hydroxyl group. These compounds are of some utility as heteropolar agents.
- polar groups those which may be considered as being derived from an acid.
- the polar groups of this class can be designated as polar or lipophobic residues of acids.
- esters of phosphorus-containing acids include ortho, meta and pyrophosphoric acid, ortho phosphorous acid and hypophosphoric acid as well as these acids in which one or more oxygen atoms have been replaced by sulfur or selenium.
- esters I mean to include both neutral and acid esters, mixed esters and the acid halide esters.
- phosphorus-containing esters in view of their excellent properties, may find application for numerous purposes such as, for example, agents preventing the spattering of oils, as ingredients in boring and cutting oils, as ingredients in rust removerand metal cleaners, as ingredients in insecticides, fungicides and the like, as agents to improve ore flotation, as detergents, as wetting, dispersing, and emulsifying agents, as corrosion inhibitors, as lubricants or addition agents to lubricants for extreme pressure lubrication, etc.
- agents preventing the spattering of oils as ingredients in boring and cutting oils, as ingredients in rust removerand metal cleaners, as ingredients in insecticides, fungicides and the like, as agents to improve ore flotation, as detergents, as wetting, dispersing, and emulsifying agents, as corrosion inhibitors, as lubricants or addition agents to lubricants for extreme pressure lubrication, etc.
- esters of the phosphorus-containing esters those containing sulfur, i. e., esters of thio acids of phosphorus, and more particularly, the esters of the ortho thio acids are endowed with particularly valuable properties.
- heteropolar compounds having certain unusually desirable properties may be prepared from the present alcohols by reacting them with sulfating, sulfiting, sulfonating, or sulfinating agents, polybasic carboxylic acids, etc., and by ester interchange with the lower alkyl esters of boric, arsenic, arsenous, acids etc.
- the alcohols may be reacted with sulfuric acid, sulfurous acid, naphthalene sulfonic acid, amido sulfonic acid, chlorsuli'onic acid, sulfurylchloride, organic sulfamic acids, amino sulfonic acid, amino sulfonates, imino disulfonic acid salts, citric acid, succinic acid, lower alkyl a but not limited by the following examples:
- Methyl propyl ketone is condensed with itself by refluxing over calcium carbide.
- the product consists of unreacted methyl propyl ketone and 4-methyl-nonene-4-one-6, with a small amount of isomeric alpha beta dimers and trlmers.
- the condensation products are charged, along with about 1% of sodium ethoxide, into a suitable fractionating apparatus.
- the mixture is brought to boiling, held under total reflux for a few minutes, and then fractionated while maintaining the stillhead temperature below the boiling point .of the 4-methyl-nonene-4-one-6 (195.5 C. at 160 mm.) In the absence of a rearrangement catalyst, the fractionation will be very slow.
- the distillate consists essentially of 4-methyl-nonene- 3-one-6.
- the stillhead temperature may be allowed to rise to the boiling point of the doubly unsaturated beta gamma, beta gamma trimer which may be collected separately. During this latter operation it is preferable to conduct the rearrangement and fractionation under a diminished pressure.
- Example H Illustrating the relative ease of hydrogenation of a beta gamma unsaturated ketone as compared to an alpha beta unsaturated ketone.
- a mixture consisting essentially of 77% 3-methyl-heptene-3-one-5 and 22% isomeric twelve carbon alpha beta, alpha beta doubly unsaturated ketones is hydrogenated in the liquid phase for 183 minutes at 500 lbs. per square inch pressure and at 151 C. to 175 C. using a nickel catalyst.
- the product is found to contain only 2.3% of alcohol, the remainder being saturated ketone and a small amount of hydrocarbon. Under more drastic conditions the yield of alcohol may be increased, but only at the expense of an increased yield of hydrocarbon.
- the same mixture is subjected to a rearrangement treatment as above described, the dimer being collected separately.
- the dimer fraction consisting essentially of 3-methyl-heptene-2- one-5 upon hydrogenation for 245 minutes at 500 lbs. per square inch pressure and at 149 to 200 C. using a nickel catalyst yields from 85 to 94% 3-methyl-heptanol-5.
- Example 111 Illustrating the preparation of a material suitcooled mixture is slowly added a one-third molar quantity of POCla. After completion of the reaction, the pyridine salt is removed and the benzol solution washed with dilute hydrochloric acid and with water. After removing the benzol by evaporation or distillation, the neutral trialkyl phosphate remains.
- the product has the structural formula O:PE(OR)3 wherein R.
- a quantity of 3,7,9-trimethyl undecanoL-B is converted to the aluminate by any of the known methods, as, for instance, by the metathetic reaction with aluminum ethoxide.
- the higher alcohol aluminate is dissolved in a suitable solvent, the solution cooled to about C. and there is slowly added thereto with stirring a CS2 solution containing a one-third molar equivalent of PSCla while maintainingthe temperature at approximately 10 C. After allowing time for the reaction to come to completion any unused PSCla and the A1013 are hydrolyzed and the hydrocarbon phase washed with water, filtered, and the product finally recovered by distilling off the solvent.
- This product and other products having the structure S P::(OR)3 wherein R represents a secondary branched chain alkyl radical, are superior to the neutral esters of the type shown in Example Ill when used as addition agents in lubricants.
- the neutral thio esters of this type are notably less viscous and have superior solubility in most lubricants.
- the properties of a heteropolar compoundof the type may be tempered to fit a particular need by the introduction of one or two lipophile groups of a difierent character, such as, for instance, a short chain alkyl group or groups to enhance the wetting power or solubility, a phenolic group or groups to control solubility or heat stability, etc.
- a difierent character such as, for instance, a short chain alkyl group or groups to enhance the wetting power or solubility, a phenolic group or groups to control solubility or heat stability, etc.
- Suitable lipophile groups which may be used in conjunction with the present secondary branched lipophile group or groups of difierent character.
- the second appropriate agent such as, forexample, diethylene glycol, phenol, amyl mercaptan, etc. If it is desired to prepare a mixed neutral ester the last reagent yielding the desired lipophile group is preferably added in a moderate, excess.
- the acid esters of thiophosphoric acid are for many purposes superior to the corresponding.
- Example V Illustrating the preparation. of a dialkyl ester of dithiophosphoric acid.
- a quantity of 3-methyl-heptanol-5 in excess I is added slowly and with stirring to a suspension of P285 in benzene or toluene, holding the temperature at preferably about 50 C. After the apparent completion of the reaction, the solution is refluxed for several hours. Upon removing the solvent by distillation the impure product remains as a residue. Bjaidessmall amounts of impurities from the P285 and excess alcohol, there exists a small amount of a compound having presumably the structure on where R represents the secondary branched chain lipophile radical.
- the main product, which has the structure may be recovered by any of the known purification methods. In the form of its alkali metal salts it is moderately water-soluble, capillary active and exerts a mild detergent action.
- Example VI Ifllustrating the preparation of a trialkyl phospentanol-3, when converted to the sodium alcoholate and reacted with a one-third molar equivalent of PCla, according to the well known pro-.
- Acid heteropolar compounds find their widest application in the form of their salts. In such cases, a further means of adjusting the heteropolar compound to give the maximum emciency is through the proper choice of a salt-forming agent. While any of the salt-forming alkaline agents such as alkali and alkaline earth bases, alkyl amines, dialkylamines, trialkylamines, alkyl diamines, aryl amines, diarylamines, thio aryl amines, aryl hydrazines, aralkyl amines, certain pyridines, pyrol and alkaloid derivatives, etc., may be used, the properties of the heteropolar compounds are considerably affected by the character of the salt-forming cation and the proper choice of salt-forming agent is entirely dependent upon the use for which the heteropolar compound is designed. In the i'oregoing and in the claims when referring to a heteropolar compound" or an ester, which terms cover the acid as well as the neutral esters, I
- a heteropolar compound from an unsaturated ketone the steps of rearranging an alpha beta unsaturated ketone to the isomeric beta gamma unsaturated ketone, hydrogenating the beta gamma unsaturated ketone to a saturated secondary alcohol, and reacting said alcohol with an agent capable of attaching thereto in lieu of the hydroxyl group a lipophobic residue of a phosphorus-containing acid.
- An ester of a thio phosphorus-containing acid containing at -least one branched chain aliphatic lipophile group of at least seven carbon atoms attached by a secondary carbon atom to an oxygen atom which, in turn, is linked to a phosphorus atom.
- An ester 01' a phosphorus-containing acid containing at least one aliphatic lipophile group attached to phosphorus through oxygen by a secondary carbon atom which, in turn, is attached to at least one aliphatic group containing a forked chain.
- An ester of a phosphorus-containing acid containing at least one branched chain aliphatic lipophile group of at least seven carbon atoms attached by a secondary carbon atom to an oxygen atom which, in turn, is linked to a phosphorus atom.
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Description
Patented Apr. 16, 1940 UNITED STATES PROCESS AND PRODUCT RELATING TO HETEBOPOLAR COMPOUNDS Franklin A. Bent, Berkeley, Calif" assignor to Shell Development Company, San Francisco, Calif., a corporation of Delaware No Drawing. Application December 27, 1937,
Serial No. 182.005
. 17 Claims.
The present invention relates to a' process for the preparation of, and products constituting, a lbroad class of heteropolar (polar-nonpolar) compounds ranging'from' neutral oil-soluble compounds to acidic or basic water-soluble compounds which have the common property of exhibiting a certain duo-nature. This duo-nature is manifested by an affinity on the one hand for lipins and by an affinity for water or inorganic substances on the other hand, caused by the simultaneous presence of lipophile and polar or lipophobe groups in the molecule.
More particularly, the invention concerns a process for the preparation of, and products relating to heteropolar compounds in which at least one lipophile radical is predominantly of aliphatic character, and more particularly to those compounds containing an aliphatic lipophile radical or radicals of highly branched structure.
Compounds of this type, although varying considerably with the nature and size of the lipophile and polar or lipophobe groups tend, in general, to cling tenaciously on metal and certain inorganic surfaces, to lower the surface tension of water or aqueous liquids when dissolved therein, etc., and consequently, are suited for numerous purposes where tenacity, wetting power, penetration, etc., are factors, such as, for example, in the lubricant, flotation, textile, leather, and many other industries.
An object of the present invention is to provide an improved method for the production of a superior class of heteropolar compounds having at least one lipophile radical, said lipophile radical having the structure hereinafter set forth. A
further object of the invention is to provide new a polar group are, in general, superior in many respects to similar heteropolar compounds in which the lipophile groups are normal. The
superior qualities of this class of heteropolar compounds, which include a much lower viscosity and effectiveness in smaller concentrations, are further increased if the radicals R and/or R are of a forked chain structure.
It is tound that this preferable type of compound may be economically prepared in accordance with the present improved method which consists essentially of the following four steps:
(1) Preparation of an alpha beta unsaturated ketone.
(2) Rearrangement of said alpha beta unsaturated ketone to the corresponding beta gamma unsaturated ketone.
(3) Hydrogenation of said beta gamma unsaturated ketone to form the corresponding saturated secondary alcohol.
(4) Reaction of said saturated secondary alcohol with a suitable reagent whereby there is attached to the molecule in lieu of the hydroxyl group a lipophoblc residue of an acid.
By an alpha beta unsaturated ketone is meant a ketone containing an ethylene linkage attached to the carbonyl group. These ketones contain a conjugated system of the structure By a beta gamma unsaturated ketone is meant a ketone containing an ethylene linkage attached to the carbonyl group through a methylene group. These ketones contain the structural grouping The alpha beta unsaturated ketones applicable in the present process may be designated by the general formula:
H g R; Bz-(: -(F=(IJ-CC:I I R: R: R4 R1 wherein R1 through R1 may be any member of the group consisting of hydrogen, aliphatic and .cyclo-parafiinic groups, with the provisions that C and or C be tertiary carbon at0m(s), and
Gil
that the sum of the carbon atoms in R1, 2 and a 'be not less than two. These applicable alpha beta unsaturated ketones, it is seen, contain at least seven carbon atoms. Examples of structures containimz mple R1, R2 and R3 radicals are Hr-CH:
at. cm
- CHECK! (came-c CHr-CH:
Moreover, R2 may be connected with R1 or Rs by one or more methylene groups to form a polymethylene ring structure, for example, containing the groupings.
CHa-CH: R|
Likewise compounds in which Re is connected to v R1 or R4 by one or more methylene groups are also applicable. Examples of this structure are a s c CHz-CH:
These applicable alpha beta unsaturated ketones, including their optical and stereo-isomers, constitute a class of unsaturated ketones diflering in several respects from other unsaturated ketones. One notable characteristic of these compounds is the ease with which they may be alkylated. Unsaturated ketones of other structure, such as mesityl oxide, ethyl nonenone gamma delta, 3-methyl-cyclohexadienyl-2, fi-acetone, etc., which are not allwlated under mild conditions are not applicable.
Unsaturated ketones of the desired structure may be prepared by any one of several known methods, the invention being independent of the mode of formation. One suitable method is through the condensation of ketones followed by dehydration of 'the resulting ketols. The reactions involved in the synthesis are illustrated by the case of the formation of 2, 4, 8-trimethylnonene-4-one-6 from methyl isobutyl ketone.
Am aliphatic, alicyclic orvaliphatic alicyclic ketone having a primary or secondary alpha carbon atom, such as, for example, methyl ethyl ketone, methyl isopropyl ketone, methyl cyclohexyl ketone, ethyl cyclopentyl ketone, cyclohexanone, cyclopentanone, alpha methyl cyclopentanone, etc., may be employed to form the starting material of my process. Any suitable catalyst such as CaCz, A1203, NaOCrHa, POCls, H2804, HCl, IIBr, HI, CaO, ThOz, ZnClz, Na, aluminum halide, organo magnesium halide, sodium pyrosulfate, sodamide, triphenyl aluminum, etc., may be used to accelerate the reaction. In most cases the two reactions proceed under the same conditions to yield the desired alpha beta unsaturated ketone directly. If under mild (usually alkaline conditions) the ketol is obtained, this may be easily dehydrated by heating with a little acid. In this method of preparation all theoretically possible condensation products are formed to a certain extent, their relative quantity being determined by the ketone, catalyst, and conditions used. Thus, for example,
when condensing methyl ethyl ketone with itself 3-methyl heptene-3-one-5, 3, 4-dimethyl hexene- 3-one-5, 3, 6, 'l-trimethyl nonadiene-3, 6-one-5, and 3, 4, l-trimethyl nonadiene-3, 6-one-5 may be isolated. With A1203 as a catalyst, for example, 3-methy1 heptene-3-one-5 is the predominant product, while with acid catalysts 3, 4-dimethyl-hexene-3-one-5 predominates. The alpha beta, alpha beta doubly unsaturated trimer which is also applicable may be separated from the reaction product by fractionation, although this step is not necessary.
Another and convenient method for preparing the desired alpha beta unsaturated ketones is through the condensation of a ketone of the above-mentioned class with an alpha substituted aldehyde. Any aldehyde having the structure Another method of producing the desired alpha beta unsaturated ketones is through the dehydration of the corresponding acyloins. This may be accomplished according to the scheme rearranges CH: CH:
If it is attempted to perform the reduction in accordance with accepted commercial hydrogenation methods, it is found that severe conditions are required and that the yields are then poor due to the simultaneous formation 'of considerable amounts of hydrocarbons and saturated ketone. Since the product is very impure, it must be subjected to a fractionation, usually under vacuum, to separate the desired secondary alcohol from the unreacted material, saturated ketones and hydrocarbons. This difllculty in hydrogenation is no doubt due to coniugation in the alpha beta unsaturated ketones,
On the other hand, the corresponding beta gamma unsaturated ketones undergo hydrogenation under more favorable conditions and in a cleancut manner to yield the corresponding secondary alcohols in excellent yields. The beta gamma ketones differ further from their corresponding alpha beta ketones in showing essentially no exalted molecular refractions and having lower melting points, boiling points, refractive indices and densities.
In accordance with the present invention, I therefore rearrange the alpha beta unsaturated ketone, regardless of source, to the corresponding beta gamma imsaturated ketone before effecting hydrogenation.
The tertiary carbon atoms (0* and/or C in the above-mentioned alpha beta unsaturated ketone structure counteract to a certain extent the tendency of the unsaturated bonds to conjugate, i. e., to form static alpha beta unsaturated ketones. This counteracting tendency manifests itself in the formation of an equilibrium mixture at alpha beta and beta gamma unsaturated ketone in which the beta gamma ketone content may range from traces to an appreciable amount depending upon the size and character of the radicals, R1, 2, 3, and 4. Although it usually requires a considerable time for equilibrium to become established under normal conditions, a few unsaturated ketones of the above structure equilibrate quite rapidly and therefore make the preparation of the pure alpha beta ketone difficult. It is to be understood, however, that the formation of an equilibrium mixture containing some beta gamma ketone instead of the pure alpha beta ketone does not detrimentally affect the applicability of these compounds in the present invention.
By subjecting the alpha beta unsaturated ketone (or an equilibrium mixture of alpha beta and beta gamma unsaturated ketone) to a fractional distillation at a rate not exceeding the rate of rearrangement, the lower boiling beta gamma unsaturated ketone may be continually removed causing the rearrangement to proceed to completion. This method of producing the desired beta gamma unsaturated ketone is quite simple and generally applicable to the ketones of the above-mentioned structure,
By simply fractionating in most cases the rearrangement takes place at too slow a rate, even at elevated temperatures, to be economically practical. This may be remedied, however, by the use of a small amount of a substance which catalyzes the rearrangement, i. e., increases the mobility of the system. It is found that alkali metal alkoxides in particular, such as the various alcoholates of sodium, lithium, potassium, aluminum, magnesium, etc., are suited. Other catalysts, such as alcoholic alkali and even mineral acid may sometimes be used.
Although the catalysts are usually effective in very small amounts, it is found that the rate of rearrangement is somewhat dependent upon the amount 01 catalyst present, being somewhat higher at catalyst concentration of about 3 to 5%. While the lower boiling alpha beta unsaturated ketones are conveniently rearranged at their normal boiling points, such high molecular weight unsaturated ketones as are unstable at their normal boiling points may be rearranged at a somewhat lower temperature by carrying out the rearrangement under a suitably diminished pressure.
As has been previously shown, the preparation of any desired alpha beta unsaturated ketone is usually accompanied by the formation of a small amount of other condensation products. .Since these products usually consist of isomeric alpha beta unsaturated ketones and alpha beta unsaturated ketones of different molecular weight they may beqearranged to their corresponding beta gamma unsaturated ketones in the same manner and are suitable for the preparation of valuable heteropolar compounds, However, since heteropolar compounds consisting of a single compound or a mixture of closely relatedisomers are in most cases far superior to any mixture of compounds, it is usually desirable to separate the various products before attaching the polar groups. This separation, which may be neglected if desired, may be efiected at any one of three stages in the preparation, namely, previous to the rearranging, during the rearranging, or after the hydrogenation. Since in the rearrangement step the'material is subjected to a slow fractionation, the separation is most conveniently carried out during this operation, it being 'merely necessary to collect the promptly as possible. Since, however, in the maof from 1 to of an active hydrogenation catalyst such as nickel, using about 500 lbs. per square inch pressure and a temperature of about 150 C. However, other conditions including temperatures from 60 C. to about 250 C., pres-.
sure from one to over IOU atmospheres, the use of solvents and a wide variety of catalysts may be resorted to. Vapor phase hydrogenation, although applicable in many cases, is not as practical as the liquid phase hydrogenation and therefore not preferred. Any traces of sulfur tending to poison the catalyst may be removed previous to hydrogenation by first subjecting the beta gamma unsaturated ketone to a treatment with copper hydrate, spent catalyst or some other suitable agent in the known manner.
It is seen that by the proper choice of the ketones, aldehydes or esters used as starting materials, the condensation catalysts employed,
any,- of the common polar groups, certain polar groups are more practical than others. For example, the polar groups Cl, Br, --I, SH, CN and NO: are not easily attached to the present lipophile groups and moreover form heteropolar compounds of very restricted utility. Likewise, the. unsaturated ketones contain the polar carbonyl group, and are in reality heteropolar compounds. Due to-the weakness of the polar group and the unfavorable balance of these compounds, they are, however, of practically no value as h'eteropolaragents. The secondary alcohols of the present'invention are likewise hateropolar compounds, since they contain the polar hydroxyl group. These compounds are of some utility as heteropolar agents.
By far the most important class of polar groups are those which may be considered as being derived from an acid. The polar groups of this class can be designated as polar or lipophobic residues of acids.
One class of heteropolar compounds readilyprepared according to the present invention consists of esters of phosphorus-containing acids. By phosphorus-containing acids I mean to include ortho, meta and pyrophosphoric acid, ortho phosphorous acid and hypophosphoric acid as well as these acids in which one or more oxygen atoms have been replaced by sulfur or selenium. By esters, I mean to include both neutral and acid esters, mixed esters and the acid halide esters.
These phosphorus-containing esters, in view of their excellent properties, may find application for numerous purposes such as, for example, agents preventing the spattering of oils, as ingredients in boring and cutting oils, as ingredients in rust removerand metal cleaners, as ingredients in insecticides, fungicides and the like, as agents to improve ore flotation, as detergents, as wetting, dispersing, and emulsifying agents, as corrosion inhibitors, as lubricants or addition agents to lubricants for extreme pressure lubrication, etc.
Of the phosphorus-containing esters, those containing sulfur, i. e., esters of thio acids of phosphorus, and more particularly, the esters of the ortho thio acids are endowed with particularly valuable properties.
Other classes of heteropolar compounds, having certain unusually desirable properties may be prepared from the present alcohols by reacting them with sulfating, sulfiting, sulfonating, or sulfinating agents, polybasic carboxylic acids, etc., and by ester interchange with the lower alkyl esters of boric, arsenic, arsenous, acids etc. For example, the alcohols may be reacted with sulfuric acid, sulfurous acid, naphthalene sulfonic acid, amido sulfonic acid, chlorsuli'onic acid, sulfurylchloride, organic sulfamic acids, amino sulfonic acid, amino sulfonates, imino disulfonic acid salts, citric acid, succinic acid, lower alkyl a but not limited by the following examples:
Erampie I Illustrating the rearrangement of a; simple alpha beta unsaturated ketone to the corresponding beta gamma unsaturated ketone.
Methyl propyl ketone is condensed with itself by refluxing over calcium carbide. The product consists of unreacted methyl propyl ketone and 4-methyl-nonene-4-one-6, with a small amount of isomeric alpha beta dimers and trlmers. After distilling oif the unreacted methyl propyl ketone, the condensation products are charged, along with about 1% of sodium ethoxide, into a suitable fractionating apparatus. The mixture is brought to boiling, held under total reflux for a few minutes, and then fractionated while maintaining the stillhead temperature below the boiling point .of the 4-methyl-nonene-4-one-6 (195.5 C. at 160 mm.) In the absence of a rearrangement catalyst, the fractionation will be very slow. The distillate consists essentially of 4-methyl-nonene- 3-one-6.
Upon the completion of the rearrangement and removal of the ten carbon unsaturated ketones, the stillhead temperature may be allowed to rise to the boiling point of the doubly unsaturated beta gamma, beta gamma trimer which may be collected separately. During this latter operation it is preferable to conduct the rearrangement and fractionation under a diminished pressure.
Example H Illustrating the relative ease of hydrogenation of a beta gamma unsaturated ketone as compared to an alpha beta unsaturated ketone.
A mixture consisting essentially of 77% 3-methyl-heptene-3-one-5 and 22% isomeric twelve carbon alpha beta, alpha beta doubly unsaturated ketones is hydrogenated in the liquid phase for 183 minutes at 500 lbs. per square inch pressure and at 151 C. to 175 C. using a nickel catalyst. The refractive index changes during hydrogenation from 1.456017/D to 1.4394-165/1) after which the reaction virtually ceases. The product is found to contain only 2.3% of alcohol, the remainder being saturated ketone and a small amount of hydrocarbon. Under more drastic conditions the yield of alcohol may be increased, but only at the expense of an increased yield of hydrocarbon.
The same mixture is subjected to a rearrangement treatment as above described, the dimer being collected separately. The dimer fraction, consisting essentially of 3-methyl-heptene-2- one-5 upon hydrogenation for 245 minutes at 500 lbs. per square inch pressure and at 149 to 200 C. using a nickel catalyst yields from 85 to 94% 3-methyl-heptanol-5.
Example 111 Illustrating the preparation of a material suitcooled mixture is slowly added a one-third molar quantity of POCla. After completion of the reaction, the pyridine salt is removed and the benzol solution washed with dilute hydrochloric acid and with water. After removing the benzol by evaporation or distillation, the neutral trialkyl phosphate remains.
In the above example, the product has the structural formula O:PE(OR)3 wherein R.
represents the branched chain secondary alcohol ester radical. The monoor dialkyl esters having the structures /OR 0=P=Ch and 0=P=(0B)r Cl or upon hydrolysis of the chlorine atoms on 0R), 0= and 0:1
(OH): OH
Illustrating the preparation of a material particularly suitable for imparting oiliness and high pressure characteristic to lubricants.
A quantity of 3,7,9-trimethyl undecanoL-B is converted to the aluminate by any of the known methods, as, for instance, by the metathetic reaction with aluminum ethoxide. The higher alcohol aluminate is dissolved in a suitable solvent, the solution cooled to about C. and there is slowly added thereto with stirring a CS2 solution containing a one-third molar equivalent of PSCla while maintainingthe temperature at approximately 10 C. After allowing time for the reaction to come to completion any unused PSCla and the A1013 are hydrolyzed and the hydrocarbon phase washed with water, filtered, and the product finally recovered by distilling off the solvent. This product and other products having the structure S=P::(OR)3 wherein R represents a secondary branched chain alkyl radical, are superior to the neutral esters of the type shown in Example Ill when used as addition agents in lubricants. The neutral thio esters of this type are notably less viscous and have superior solubility in most lubricants.
While I have found phosphorus-containing esters containing lipophile groups of a secondary and branched chain character to be superior heteropolar agents in many respects to such compounds containing other types oi. lipophile groups, it will be appreciated that not all of the lipophile groups need be of this structure. For some particular purposes the so-called "mixed esters have been found to be the more efiicient. While still realizing the advantages of one or two lipophile groups of the present invention, the properties of a heteropolar compoundof the type may be tempered to fit a particular need by the introduction of one or two lipophile groups of a difierent character, such as, for instance, a short chain alkyl group or groups to enhance the wetting power or solubility, a phenolic group or groups to control solubility or heat stability, etc. Suitable lipophile groups which may be used in conjunction with the present secondary branched lipophile group or groups of difierent character.
are then introduced by completing the reaction with a suflicient quantity of thesecond appropriate agent, such as, forexample, diethylene glycol, phenol, amyl mercaptan, etc. If it is desired to prepare a mixed neutral ester the last reagent yielding the desired lipophile group is preferably added in a moderate, excess.
The acid esters of thiophosphoric acid are for many purposes superior to the corresponding.
oxy esters. Their comparative structures are where X represents OH, SL, or 0L, L representing any lipophile group, and R. again representing a branched chain, secondary lipophile group. These acid esters of thiophosphoric acid may be prepared in a manner'analogous to that described for the acid ow-esters, by reacting PSCla with such an amount of alcohol as is suificient to form only the mono or di esters. as the case may require.
Example V Illustrating the preparation. of a dialkyl ester of dithiophosphoric acid.
A quantity of 3-methyl-heptanol-5 in excess I is added slowly and with stirring to a suspension of P285 in benzene or toluene, holding the temperature at preferably about 50 C. After the apparent completion of the reaction, the solution is refluxed for several hours. Upon removing the solvent by distillation the impure product remains as a residue. Bjaidessmall amounts of impurities from the P285 and excess alcohol, there exists a small amount of a compound having presumably the structure on where R represents the secondary branched chain lipophile radical. The main product, which has the structure may be recovered by any of the known purification methods. In the form of its alkali metal salts it is moderately water-soluble, capillary active and exerts a mild detergent action.
Example VI Ifllustrating the preparation of a trialkyl phospentanol-3, when converted to the sodium alcoholate and reacted with a one-third molar equivalent of PCla, according to the well known pro-.
cedure for preparing aikyl phosphites, yields an interesting and novel material having presumably the structure When reacting the alcohol directly with P613 without first converting to the alcoholate, a considerable quantity of acid ester chlorides are formed which on hydrolysis yield acid esters having the structure P= on \OR and appropriate esters with concentrated sulfuric acid, sulphur, etc., in the known manner, interesting compounds may be prepared having the in which R represents a lipophilegroup having at least in one instance the saturated, secondary, branched chain structure as hereinbefore described.
Acid heteropolar compounds find their widest application in the form of their salts. In such cases, a further means of adjusting the heteropolar compound to give the maximum emciency is through the proper choice of a salt-forming agent. While any of the salt-forming alkaline agents such as alkali and alkaline earth bases, alkyl amines, dialkylamines, trialkylamines, alkyl diamines, aryl amines, diarylamines, thio aryl amines, aryl hydrazines, aralkyl amines, certain pyridines, pyrol and alkaloid derivatives, etc., may be used, the properties of the heteropolar compounds are considerably affected by the character of the salt-forming cation and the proper choice of salt-forming agent is entirely dependent upon the use for which the heteropolar compound is designed. In the i'oregoing and in the claims when referring to a heteropolar compound" or an ester, which terms cover the acid as well as the neutral esters, I mean to include the various salts as well as the acid esters.
The above description is to beconstrued as illustrative only and not as limiting the invention. The different features of the invention are capable of wide variation, and such changes as are within the spirit of the invention are intended to be comprehended by the scope of the claims.
I claim as my invention:
1. In a process for the production of a heteropolar compound from an unsaturated ketone, the steps of rearranging an alpha beta unsaturated ketone to the isomeric beta gamma unsaturated ketone, hydrcgenating the beta gamma unsaturated ketone to a saturated secondary alcohol, and reacting said alcohol with a sulfating agent.
2. In a process for the production of a heteropolar compound from an unsaturated ketone, the steps of rearranging an alpha beta unsaturated ketone to the isomeric beta gamma unsaturated ketone, hydrogenating the beta gamma unsaturated ketone to a saturated secondary alcohol, and reacting said alcohol with P0013.
3. In a process for the production of a heteropolar compound from an unsaturated ketone, the steps of rearranging an alpha beta unsaturated ketone to the isomeric beta gamma unsaturated ketone, hydrogenating the beta gamma unsaturated ketone to a saturated secondary alcohol and reacting said alcohol with PSCla.
4. In a process for the production of a heteropolar compound from an unsaturated ketone, the steps of rearranging an alpha beta unsaturated ketone to the isomeric beta gamma unsaturated ketone, hydrogenating the beta gamma unsaturated ketone to a saturated secondary alcohol, and reacting said alcohol with an agent capable of attaching in lieu of the hydroxyl group a lipophobic residue of a thio-phosphorus-containing acid.
5. In a process for the production of a heteropolar compound from an unsaturated ketone, the steps of rearranging an alpha beta unsaturated ketone to the isomeric beta gamma unsaturated ketone, hydrogenating the beta gamma unsaturated ketone to a saturated secondary alcohol, and reacting said alcohol with an agent capable of attaching thereto in lieu of the hydroxyl group a lipophobic residue of a phosphorus-containing acid.
6. In a process for the production of a heteropolar compound from an unsaturated ketone, the steps of rearranging an alpha beta unsaturated ketone to the isomeric beta gamma unsaturated ketone, hydrogenating the beta gamma unsaturated ketone to a saturated secondary alcohol and reacting said secondary alcohol with an agent capable of attaching thereto in lieu of the .hydroxyl group a lipophobic residue of a sulfurcontaining acid.
7. In a process for the production of a heteropolar compound from an unsaturated ketone, the steps of. rearranging an alpha beta unsaturated ketone to the isomeric beta gam a unsaturated ketone, hydrogenating the beta gamma unsaturated ketone to a saturated secondary alcohol, and reacting said secondary alcohol with an agent capable of attaching thereto in lieu of the hydroxyl group a lipophobic residue of an acid of an element of the amphoteric group consisting of sulfur, phosphorus, silicon, arsenic and boron.
8. In a process for the production of a heteropolar compound from an unsaturated ketone, the steps of rearranging an alpha beta unsaturated ketone to the isomeric beta gamma unsaturated ketone, hydrogenating the beta gamma unsaturated ketone to a saturated secondary alcohol, and reacting said secondary alcohol with an agent capable of attaching thereto in lieu of. the hydroxyl group a lipophobic residue of an acid.
9. In a process for the production of a heteropolar compound from an unsaturated ketone, the steps of rearranging an alpha beta unsaturated ketone to the isomeric beta gamma unsaturated ketone, and hydrogenating the latter to a saturated secondary alcohol.
10. An ester of a dithio-phosphoric acid containing at least one branched chain aliphatic lipophile group attached by a secondary carbon atom to an oxygen atom which, in turn, is linked to a phosphorus atom.
11. An ester of a thio-phosphoric acid containing at least one branched chain aliphatic lipophile group attached by a secondary carbon atom to an oxygen atom which, in turn, is linked to a phosphorus atom.
12. An ester of a phosphorus acid containing at least one branched chain aliphatic lipophile group attached by a secondary carbon atom to an oxygen atom which, in turn, is linked to a phosphorus atom.
13. An ester of a phosphoric acid containing at least one branched chain aliphatic lipophile roup attached by a secondary carbon atom to an oxygen atom which, in turn, is linked to a phosphorus atom.
14. An ester of a thio phosphorus-containing acid containing at least one aliphatic lipophile group attached to phosphorus through oxygen by a secondary carbon atom which, in turn, is attached to at least one aliphatic group containing a forked chain.
15. An ester of a thio phosphorus-containing acid containing at -least one branched chain aliphatic lipophile group of at least seven carbon atoms attached by a secondary carbon atom to an oxygen atom which, in turn, is linked to a phosphorus atom.
16. An ester 01'. a phosphorus-containing acid containing at least one aliphatic lipophile group attached to phosphorus through oxygen by a secondary carbon atom which, in turn, is attached to at least one aliphatic group containing a forked chain.
17. An ester of a phosphorus-containing acid containing at least one branched chain aliphatic lipophile group of at least seven carbon atoms attached by a secondary carbon atom to an oxygen atom which, in turn, is linked to a phosphorus atom.
FRANKLIN A BENT.
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US212979A US2246032A (en) | 1937-12-27 | 1938-06-10 | Process for the production of beta gamma unsaturated ketones |
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Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2435403A (en) * | 1942-04-30 | 1948-02-03 | Shell Dev | Cyclic alcohols and their preparation |
US2566957A (en) * | 1946-05-06 | 1951-09-04 | Minnesota Mining & Mfg | Tertiary-alkoxy chlorosilanes |
US2567154A (en) * | 1948-06-26 | 1951-09-04 | Monsanto Chemicals | Tetra-alkylmonothionopyrophosphate and process of preparation |
US2566956A (en) * | 1942-12-31 | 1951-09-04 | Minnesota Mining & Mfg | Tertiary-alkoxy chlorosilanes |
US4010205A (en) * | 1973-12-07 | 1977-03-01 | Firmenich S.A. | Process for the preparation of a diketone derivative |
US4380674A (en) * | 1980-09-04 | 1983-04-19 | International Flavors & Fragrances Inc. | Branched ketones, organoleptic uses thereof and process for preparing same |
US4448713A (en) * | 1981-11-05 | 1984-05-15 | International Flavors & Fragrances Inc. | Branched ketones, organoleptic uses thereof and process for preparing same |
WO2017079016A1 (en) | 2015-11-06 | 2017-05-11 | The Lubrizol Corporation | Lubricant with high pyrophosphate level |
-
1937
- 1937-12-27 US US182005A patent/US2197462A/en not_active Expired - Lifetime
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2435403A (en) * | 1942-04-30 | 1948-02-03 | Shell Dev | Cyclic alcohols and their preparation |
US2566956A (en) * | 1942-12-31 | 1951-09-04 | Minnesota Mining & Mfg | Tertiary-alkoxy chlorosilanes |
US2566957A (en) * | 1946-05-06 | 1951-09-04 | Minnesota Mining & Mfg | Tertiary-alkoxy chlorosilanes |
US2567154A (en) * | 1948-06-26 | 1951-09-04 | Monsanto Chemicals | Tetra-alkylmonothionopyrophosphate and process of preparation |
US4010205A (en) * | 1973-12-07 | 1977-03-01 | Firmenich S.A. | Process for the preparation of a diketone derivative |
US4380674A (en) * | 1980-09-04 | 1983-04-19 | International Flavors & Fragrances Inc. | Branched ketones, organoleptic uses thereof and process for preparing same |
US4448713A (en) * | 1981-11-05 | 1984-05-15 | International Flavors & Fragrances Inc. | Branched ketones, organoleptic uses thereof and process for preparing same |
WO2017079016A1 (en) | 2015-11-06 | 2017-05-11 | The Lubrizol Corporation | Lubricant with high pyrophosphate level |
EP3371285B1 (en) | 2015-11-06 | 2020-01-29 | The Lubrizol Corporation | Method of lubricating a mechanical device |
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