US2309829A - Sulphur-containing esters - Google Patents
Sulphur-containing esters Download PDFInfo
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- US2309829A US2309829A US358697A US35869740A US2309829A US 2309829 A US2309829 A US 2309829A US 358697 A US358697 A US 358697A US 35869740 A US35869740 A US 35869740A US 2309829 A US2309829 A US 2309829A
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- Prior art keywords
- hydrocarbons
- wax
- chlorine
- monochloro
- mixture
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title description 19
- 239000005864 Sulphur Substances 0.000 title description 11
- 150000002148 esters Chemical class 0.000 title description 4
- 239000001993 wax Substances 0.000 description 75
- 229930195733 hydrocarbon Natural products 0.000 description 59
- 150000002430 hydrocarbons Chemical class 0.000 description 59
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 35
- 239000000203 mixture Substances 0.000 description 29
- 229910052801 chlorine Inorganic materials 0.000 description 28
- 239000000460 chlorine Substances 0.000 description 28
- 238000000034 method Methods 0.000 description 21
- 238000005660 chlorination reaction Methods 0.000 description 20
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 17
- 239000000463 material Substances 0.000 description 15
- 239000004215 Carbon black (E152) Substances 0.000 description 13
- 125000003963 dichloro group Chemical group Cl* 0.000 description 13
- 150000008282 halocarbons Chemical class 0.000 description 13
- 238000002844 melting Methods 0.000 description 13
- 230000008018 melting Effects 0.000 description 13
- 150000001298 alcohols Chemical class 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 9
- 229910052736 halogen Inorganic materials 0.000 description 8
- 150000002367 halogens Chemical class 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 239000012188 paraffin wax Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- -1 monochlor compound Chemical class 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000008096 xylene Substances 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- WQYSXVGEZYESBR-UHFFFAOYSA-N thiophosphoryl chloride Chemical compound ClP(Cl)(Cl)=S WQYSXVGEZYESBR-UHFFFAOYSA-N 0.000 description 5
- 239000012991 xanthate Substances 0.000 description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical class [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 4
- 230000002140 halogenating effect Effects 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 150000002576 ketones Chemical class 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 4
- RZJRJXONCZWCBN-UHFFFAOYSA-N octadecane Chemical compound CCCCCCCCCCCCCCCCCC RZJRJXONCZWCBN-UHFFFAOYSA-N 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 150000001805 chlorine compounds Chemical class 0.000 description 3
- 125000001309 chloro group Chemical group Cl* 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 150000004820 halides Chemical class 0.000 description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 3
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 3
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical class FF PXGOKWXKJXAPGV-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
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 241001647090 Ponca Species 0.000 description 2
- RYYWUUFWQRZTIU-UHFFFAOYSA-N Thiophosphoric acid Chemical class OP(O)(S)=O RYYWUUFWQRZTIU-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000003518 caustics Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- XQNIYBBHBZAQEC-UHFFFAOYSA-N diphosphorus trisulphide Chemical compound S=PSP=S XQNIYBBHBZAQEC-UHFFFAOYSA-N 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 229910052731 fluorine Chemical class 0.000 description 2
- 239000011737 fluorine Chemical class 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 150000002497 iodine compounds Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229940038384 octadecane Drugs 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 150000002926 oxygen Chemical class 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 125000005323 thioketone group Chemical group 0.000 description 2
- 150000004764 thiosulfuric acid derivatives Chemical class 0.000 description 2
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 1
- QKUNKVYPGIOQNP-UHFFFAOYSA-N 4,8,11,14,17,21-hexachlorotetracosane Chemical compound CCCC(Cl)CCCC(Cl)CCC(Cl)CCC(Cl)CCC(Cl)CCCC(Cl)CCC QKUNKVYPGIOQNP-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- GFVUWETXLKDTIO-UHFFFAOYSA-J [C+4].[SH-].[SH-].[SH-].[SH-] Chemical class [C+4].[SH-].[SH-].[SH-].[SH-] GFVUWETXLKDTIO-UHFFFAOYSA-J 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- SKOLWUPSYHWYAM-UHFFFAOYSA-N carbonodithioic O,S-acid Chemical compound SC(S)=O SKOLWUPSYHWYAM-UHFFFAOYSA-N 0.000 description 1
- SURLGNKAQXKNSP-DBLYXWCISA-N chlorin Chemical compound C\1=C/2\N/C(=C\C3=N/C(=C\C=4NC(/C=C\5/C=CC/1=N/5)=CC=4)/C=C3)/CC\2 SURLGNKAQXKNSP-DBLYXWCISA-N 0.000 description 1
- 150000001804 chlorine Chemical class 0.000 description 1
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 1
- FDSGHYHRLSWSLQ-UHFFFAOYSA-N dichloromethane;propan-2-one Chemical compound ClCCl.CC(C)=O FDSGHYHRLSWSLQ-UHFFFAOYSA-N 0.000 description 1
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical compound CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- 230000026045 iodination Effects 0.000 description 1
- 238000006192 iodination reaction Methods 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical class II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229940032007 methylethyl ketone Drugs 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- CYQAYERJWZKYML-UHFFFAOYSA-N phosphorus pentasulfide Chemical compound S1P(S2)(=S)SP3(=S)SP1(=S)SP2(=S)S3 CYQAYERJWZKYML-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000000638 solvent extraction Methods 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
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 230000035900 sweating Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
Classifications
-
- 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
- C07F9/17—Esters of thiophosphoric acids with hydroxyalkyl compounds without further substituents on alkyl
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C329/00—Thiocarbonic acids; Halides, esters or anhydrides thereof
Definitions
- Our invention relates to a method of synthesizing sulphur-bearing derivatives of high molecular weight hydrocarbons and more particularly to a method of synthesizing relatively pure high molecular weight sulphur compounds from parafiin hydrocarbons.
- One object of our invention is to provide a method for synthesizing relatively pure high molecular weight sulphur compounds from petroleum hydrocarbons.
- Another object of our invention is to provide a method for converting petroleum fractions and similar hydrocarbons of low value into high molecular weight sulphur compounds of great commercial value.
- a further object of our invention is to provide a method of synthesizing high molecular weight sulphur compounds from parafiin hydrocarbons.
- the first (least soluble) portion consisting of a mixture of monochloro wax and unchlorinated wax.
- the percentage of unchlorinated wax in the original mixture was found to be 7.2 per cent.
- a tri-chloro paraffin as so-called in the prior art because of the total chlorine content. was in fact a crude mixture containing as much as 7.2 per cent of unchlorinated wax and quantities of monoand dichloro waxes, as well as trichloro wax and more highly chlorinated waxes. Its use would not give the same results as a trichloro paraffin free of higher and lower chlorinated paraffin.
- the crude chlorination mixture contains, in addition to small amounts of chlorine and hydrogen chloride and the desired monochlor wax, also unchlorinated wax and more highly chlorinated and less highly chlorinated waxes.
- the chlorination of most petroleum hydrocarbons lowers their melting points and, up to a certain point, the greater the extent of chlorination; that is, the more chlorine atoms per molecule, the lower the melting point.
- the decrease in melting point is stepwise, and this permits us to separate the unchlorinated hydrocarbons from the monochloro hydrocarbons and the monochloro hydrocarbons from the dichloro and higher chlorinated hydrocarbons.
- the temperature for the pressing operation will depend, of course, on the character of the wax used initially and will vary considerably depending on this factor. For example, at a temperature of from 80 F. to 90 F. the monochloro product formed by the chlorination of wax having a melting point of 120 F. will be liquid, while the unchlorinated wax will be solid, enabling a ready separation to be effected.
- the unchlorinated wax separated from the crude chlorination mixture may be recycled to obtain further quantities of chlorinated waxes. It does not represent refractory material, and the same proportions of chlorination products are obtained from it as from fresh wax.
- the liquid chlorinated waxes consist largely of monochloro and dichloro waxes when approximately or 20 per cent chlorine respectively is introduced into a starting wax of, say, from 115 to 130 F. melting point, but some polychloro wax may be present. These monoand dichloro waxes may be separated from each other by crystallization from acetone, using about 12 /2 gallons of acetone per 100 pounds of crude chlorinated waxes.
- an elevated temperature is employed to insure that the chloro waxes are completely dissolved in the solvent.
- the solution is then chilled to a temperature of between minus 15 F. to minus F. when a parafiin wax of 115 to 130 F. melting point is used for the initial chlorination.
- the monochloro waxes are precipitated out nearly quantitatively, while the dichloro and polychloro waxes will remain in solution.
- the precipitated monochloro waxes may be readily separated by settling, filtering, or centrifuging.
- dichloro and polychloro waxes may be similarly separated.
- the crude chlorination mixture may be separated into unchlorinated wax, monochloro wax, dichloro, and polychloro wax. It is to be understood, of course, that the separation conditions will vary depending upon the melting point of the starting material.
- monochloro wax for example, the separated monochloro wax will be found to contain approximately the theoretical chlorine content. In the case of the wax which had the F. melting point, batches showed chlorine content of 10.2 per cent, 10.5 per cent, 10.3 per cent, and 10.8 per cent. These are very close to the theoretical chlorine content of 10.0 per cent.
- This monochlor wax is substantially free from unchlorinated waxes and polychloro waxes.
- Our paraffin hydrocarbons are preferably obtained from petroleum. Any source of materials, rich in hydrocarbons of the methane or CnH2n+2 series, or mixtures relatively rich in these components, may be used as starting materials in practicing our invention.
- the method of our invention is particularly applicable to the higher parafiin hydrocarbons but is eminently satisfactory on all those hydrocarbons whose monochloro derivatives melt lower than the hydrocarbons themselves. While the product of the preferred embodiment of our invention is a mixture, the monochloro derivatives prepared according to our invention are free from unchlorinated and more highly chlorinated material.
- the dichloro derivatives are free from unchlorinated hydrocarbons, monochlorinated hydrocarbons, and more highly chlorinated hydrocarbons.
- the purity of the final product with respect to homologues is determined by the purity of the starting hydrocarbon. It is understood, of course, that when a pure hydrocarbon is employed, a correspondingly pure halide is obtained.
- chlorine will produce substantially the equivalent of the monochloro product.
- the amount of chlorination may vary between 8 per cent and 12 per cent without being disadvantageous.
- the percentage of chlorine introduced into the hydrocarbon just described will be approximately 17 per cent when a dichloro product is desired.
- the amount of chlorine introduced will be less in the case of the high molecular weight, higher melting hydrocarbons, and more in the case of the lower molecular weight, lower melting hydrocarbons, for a given number of chlorine atoms per molecule.
- the chlorination may be accomplished in any suitable manner.
- Dichloro waxes and polychloro waxes prepared according to our method are suitable for use in any of the applications described in the prior art, where such dichloro waxes and polychloro waxes are required. Since they contain no unchlorinated wax or lower chlorinated waxes, they are particularly efiicient in these applications and are a distinct improvement over the prior art which used crude chlorination mixtures of approximately the proper chlorine content but which consisted of unchlorinated wax and more highly chlorinated wax.
- any of the halogens are suitable to make halogen derivatives of the parafiin hydrocarbons according to our method.
- This bromine, iodine, and fluorine may suitably be used to obtain the corresponding bromides, iodides and fluorides.
- the bromine compounds are much to be desired over the chlorine compounds, since they are considerably more reactive.
- we halogenate with bromine using a halogen carrier, such as halides of antimony, phosphorus, iron, various metals and the like, and separate the brominated mixture into its components as described above in the case of the chlorine compounds.
- the iodine compounds of the paraffin hydrocarbons may be prepared by direct iodination or by an indirect method.
- the indirect method the above described separation of mono-, di-, and polyhalogen derivatives maybe employed in any step of the process.
- Fluorine may be introduced into paraffln hydrocarbons directly or indirectly by analogous methods. For most purposes, however, we prefer to use the chlorine compounds on account of the cheapness and availability of chlorine above all the other halogens.
- sulfates By the action of SOzClz on the alcohols or by oxidation of sulfites.
- Thiosulfates From the sulfites and sulfur.
- Thiophosphates From the alcohols and thiophosphoryl chloride (PSCh) 6.
- Thioketones The alcohols are readily oxidized to ketones which when treated with sulfides of phosphorus yield thioketones.
- Example 1 A mixture of 386 parts of the monochlor wax prepared substantially as described above, 44 parts of caustic soda, and 400 parts of water are agitated thoroughly and heated to 400 F. under pressure for eight hours. The alcohol is separated, washed, and dried.
- Example 2 We add 368 parts of this alcohol to 60 parts of boiling thionyl chloride and maintain the temperature of the mixture at 200 F. for five hours. The sulfite is then washed with water and dried.
- Thiophosphates of the higher alcohols are produced by the action of thiophosphoryl chloride, PSCla. These products are useful addends to lubricants of all sorts.
- Example 3 We reflux a mixture of 1,100 parts of the alcohol of Example 1 with 1'70 parts of thiophosphoryl chloride in 2,000 parts of xylene for eight hours, wash with water, and then dry. On distilling oil the xylene, we obtain our higher alkyl thiophosphate.
- alkyl xanthates When refluxed with caustic alkalies and carbon bisulfides, the higher alcohols give rise to the alkyl xanthates, for example, octadecyl xanthate, pentacosyl xanthate, and the like.
- Example 4 We pass chlorine into a commercial grade of octadecane until the weight of 254 parts has increased to 290 parts.
- the crude chlorination mixture after air-blowing, is dissolved in acetone, using four times as much acetone by weight as of the chlorination mixture.
- n cooling to 40 F. most of the unchlorinated hydrocarbon separates and is removed by filtration.
- the filtrate is cooled to -20 F. and the monochlorinated hydrocarbon removed similarly. It is a liquid at room temperature.
- Example 5 We heat at 400 F. in an autoclave, 145 parts of the monchlor octadecane, 22 parts of caustic soda, and 200 parts of water at 350 F. for five hours. The octadecanol is separated, washed, and dried.
- Example 6 We dissolve 2'70 parts of octadecanol in 1,000 parts of xylene and heat with 25 parts of sodium until the latter dissolves. To the solution, we add 150 parts of carbon blsulfide and heat the mixture at 300 F. under pressure for four hours. On cooling, we wash out the sodium octadecyl xanthate with water and evaporate the solution to obtain our product.
- the high molecular weight alcohols and other oxygen derivatives of paraffin hydrocarbons may be converted into compounds in which more or less of the oxygen is replaced by sulphur. Such transformations may be accomplished by heating the oxygen derivative with phosphorus trisulfide or pentasulfide. Some of these reactions proceed without solvent, but in general it is advantageous to use an inert solvent such as benzene or xylene together with good stirring at a suitable reaction temperature. It will be apparent that the solvent must be selected so as to permit of the use of an adequate reaction temperature.
- Example 7 We heat 368 parts of the alcohol described in Example 1 to 250 F. and pass dry air through it, absorbing the water from effluent gas until 18 parts have been absorbed.
- the product is essentially the high molecular weight ketone of the same molecular weight -as the starting material.
- Example 8 Into 1,000 parts of xylene, we introduce 366 parts of the ketone of Example 7 and 100 parts of phosphorus trisulfide and boil the mixture for six hours. The solid material is filtered off and the xylene distilled from the residual thioketone.
- a method for the synthesis of sulphurbearing derivatives of high molecular weight including the steps of halogenating paraflinic hydrocarbons whose monochloro derivatives melt lower than the hydrocarbons themselves. separating relatively pure halogenated hydrocarbons from the crude halogenated mixture, hydrolyzing the pure halogenated hydrocarbon with an alkaline reagent and introducing a sulphur-bearing group by reacting the hydroxylated material with a material selected from the group consisting of thiophosphoryl chloride, thionyl chloride and sulphuryl chloride.
- a method for the synthesis of sulphurbearing derivatives of high molecular weight including the steps of halogenating paraflinic hydrocarbons whose monochloro derivatives melt lower than the hydrocarbons themselves, separating a relatively pure halogenated hydrocarbon from the crude halogenated mixture, replacing the halogen of said relatively pure halogenated hydrocarbon with hydroxyl groups by means of an alkaline reagent and introducing a sulphurbearing group by reacting the hydroxylated material with thiophosphoryl chloride.
- a method for the synthesis of sulphurbearing derivatives of high molecular weight including the steps of halogenating parafiinic hydrocarbons whose monochloro derivatives melt lower than the hydrocarbons themselves, separating a relatively pure halogenated hydrocarbon from the crude halogenated mixture, replacing the halogen of said relatively pure halogenated hydrocarbon with hydroxyl groups by means of an alkaline reagent and introducing a sulphurbearing group by reacting the hydroxylated material with thionyl chloride.
- a method for the synthesis of sulphurbearing derivatives of high molecular weight including the steps of halogenating parafiinic hydrocarbons whose monochloro derivatives melt lower than the hydrocarbons themselves, separating a relatively pure halogenated hydrocarbon from the crude halogenated mixture, replacing the halogen of said relatively pure halogenated hydrocarbon with hydroxyl groups by means of an alkaline reagent and introducing a sulphurbearing group by reacting the hydroxylated material with sulphuryl chloride.
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Description
SULPHUR-CONTAININ G ESTERS Lloyd L. Davis, Bert H. Lincoln, and Gordon D.
Byrkit, Ponca City, Okla., assignors to Continental Oil Company, Ponca City, Okla., a corporation of Delaware No Drawing. Application September 27, 1940, Serial No. 358,697
4 Claims.
Our invention relates to a method of synthesizing sulphur-bearing derivatives of high molecular weight hydrocarbons and more particularly to a method of synthesizing relatively pure high molecular weight sulphur compounds from parafiin hydrocarbons.
This application is a continuation-in-part of our copending application, Serial No. 205,530, filed May 2, 1938.
One object of our invention is to provide a method for synthesizing relatively pure high molecular weight sulphur compounds from petroleum hydrocarbons.
Another object of our invention is to provide a method for converting petroleum fractions and similar hydrocarbons of low value into high molecular weight sulphur compounds of great commercial value.
A further object of our invention is to provide a method of synthesizing high molecular weight sulphur compounds from parafiin hydrocarbons.
Other and further objects of our invention will appear from the following description.
In accordance with our invention, it is now possible to prepare relatively pure sulphur derivatives of the higher paraffin hydrocarbons without being mixed with other sulphur-containing bodies. We first prepare a relatively pure mono-, di-, or trihalogenated parafiin hydrocarbon, free from unhalogenated hydrocarbon and from each other, and convert these relatively pure halogenated hydrocarbons by chemical means into sulphur-containing derivatives.
In the prior art, references are made to monochloro parafiin, dichloro parafiin, trichloro parafiin, and the like usually considering the product of direct chlorination to be the compound represented by the total chlorine content and therefore the desired compounds. We have found that these materials are very crude mixtures of the chlorinated hydrocarbons and contain unchlorinated hydrocarbons and the mono-, di-, and polychloro derivatives and cannot be considered the desired compounds. For example, a so-called trichloro paraflin wax" containing 24 per cent chlorine, which corresponds very closely to the percentage of chlorine in the trichloro compound, was separated by means of crystallization from acetone. The first (least soluble) portion consisting of a mixture of monochloro wax and unchlorinated wax. The percentage of unchlorinated wax in the original mixture was found to be 7.2 per cent. Thus, even a tri-chloro paraffin" as so-called in the prior art because of the total chlorine content. was in fact a crude mixture containing as much as 7.2 per cent of unchlorinated wax and quantities of monoand dichloro waxes, as well as trichloro wax and more highly chlorinated waxes. Its use would not give the same results as a trichloro paraffin free of higher and lower chlorinated paraffin.
Even though the appropriate amount of chlorine is introduced in the wax to form a monochloro wax, we have found that the crude chlorination mixture contains, in addition to small amounts of chlorine and hydrogen chloride and the desired monochlor wax, also unchlorinated wax and more highly chlorinated and less highly chlorinated waxes.
In contrast to the use of such a mixture, we have found it possible, as fully described below, to obtain a relatively pure monochlor compound free from unchlorinated hydrocarbon and free from more highly chlorinated compounds. We may thus prepare (1) monohalogenated hydrocarbons substantially free from unhalogenated hydrocarbons and more highly halogenated hydrocarbons, and (2) dihalogenated hydrocarbons substantially free from unhalogenated hydrocarbons and monohalogenated hydrocarbons, as well as from halogenated hydrocarbons containing more than two atoms of halogen per molecule; (3) trihalogenated hydrocarbons free from halogenated hydrocarbons containing fewer or more than three halogen atoms per molecule and free from unhalogenated hydrocarbons. We refer in this specification to these materials as relatively pure monohalogen compounds, relatively pure dihalogen compounds, etc.
We proved the homogeneity of our relatively pure monochlor wax, for example, by chilling until approximately half of the material had solidified. Solid and liquid portions were separated by a filtration and contained 12.1 and 11.4 per cent chlorine respectively. Our monochloro wax is therefore free from both unchlorinated wax and more highly chlorinated wax. Similarly, we may prepare according to our invention diand polychloro waxes free from unchlorinated wax and monochlor wax, as well as from more highly chlorinated waxes.
The same methods as are described here in detail for the manufacture of relatively pure chlorinated wax are applicable to the manufacture of chlorine derivatives of the parafiin hydrocarbons of higher and lower molecular weight than that represented by the commonly known paraifin wax, including all those paraiiin hydrocarbons whose monochloro derivatives melt lower than the hydrocarbons themselves.
The chlorination of most petroleum hydrocarbons lowers their melting points and, up to a certain point, the greater the extent of chlorination; that is, the more chlorine atoms per molecule, the lower the melting point. The decrease in melting point is stepwise, and this permits us to separate the unchlorinated hydrocarbons from the monochloro hydrocarbons and the monochloro hydrocarbons from the dichloro and higher chlorinated hydrocarbons. We can, for example, separate the unchlorinated wax from the air-. blown mixture by filter pressing at such temperatures that all of the chlorinated waxes are largely liquids, while the unchlorinated waxes are largely solid. The temperature for the pressing operation will depend, of course, on the character of the wax used initially and will vary considerably depending on this factor. For example, at a temperature of from 80 F. to 90 F. the monochloro product formed by the chlorination of wax having a melting point of 120 F. will be liquid, while the unchlorinated wax will be solid, enabling a ready separation to be effected.
Other methods of separation, as for example, sweating, selective solvent extraction at varying temperatures and the like, may be employed for separating solid unchlorinated wax from chlorinated portions, and for separating the monochloro wax from the more highly chlorinated portions.
The unchlorinated wax separated from the crude chlorination mixture may be recycled to obtain further quantities of chlorinated waxes. It does not represent refractory material, and the same proportions of chlorination products are obtained from it as from fresh wax.
The liquid chlorinated waxes consist largely of monochloro and dichloro waxes when approximately or 20 per cent chlorine respectively is introduced into a starting wax of, say, from 115 to 130 F. melting point, but some polychloro wax may be present. These monoand dichloro waxes may be separated from each other by crystallization from acetone, using about 12 /2 gallons of acetone per 100 pounds of crude chlorinated waxes. In preparing the solution, an elevated temperature is employed to insure that the chloro waxes are completely dissolved in the solvent. The solution is then chilled to a temperature of between minus 15 F. to minus F. when a parafiin wax of 115 to 130 F. melting point is used for the initial chlorination. The monochloro waxes are precipitated out nearly quantitatively, while the dichloro and polychloro waxes will remain in solution. The precipitated monochloro waxes may be readily separated by settling, filtering, or centrifuging.
We have also used other crystallization solvents such as methyl-ethyl ketone, acetone, benzene, acetone-methylene chloride, and various halogenated solvents. The use of a particular one or combination of these solvents requires the experimental determination of the proper proportions and temperatures necessary to obtain the desired separation of the crude chlorination mixture into the various stages of chlorine contents. Halogenated solvents serve to aid in the precipitation of unchlorinated wax, while benzene increases the solubility of the more highly chlorinated materials.
On further chilling of the solution, or by evaporating off part of the solvent and again chiliing, the dichloro and polychloro waxes may be similarly separated.
In this manner, the crude chlorination mixture may be separated into unchlorinated wax, monochloro wax, dichloro, and polychloro wax. It is to be understood, of course, that the separation conditions will vary depending upon the melting point of the starting material.
In preparing monochloro wax, for example, the separated monochloro wax will be found to contain approximately the theoretical chlorine content. In the case of the wax which had the F. melting point, batches showed chlorine content of 10.2 per cent, 10.5 per cent, 10.3 per cent, and 10.8 per cent. These are very close to the theoretical chlorine content of 10.0 per cent. This monochlor wax is substantially free from unchlorinated waxes and polychloro waxes.
Our paraffin hydrocarbons are preferably obtained from petroleum. Any source of materials, rich in hydrocarbons of the methane or CnH2n+2 series, or mixtures relatively rich in these components, may be used as starting materials in practicing our invention. The method of our invention is particularly applicable to the higher parafiin hydrocarbons but is eminently satisfactory on all those hydrocarbons whose monochloro derivatives melt lower than the hydrocarbons themselves. While the product of the preferred embodiment of our invention is a mixture, the monochloro derivatives prepared according to our invention are free from unchlorinated and more highly chlorinated material. The dichloro derivatives are free from unchlorinated hydrocarbons, monochlorinated hydrocarbons, and more highly chlorinated hydrocarbons. The purity of the final product with respect to homologues is determined by the purity of the starting hydrocarbon. It is understood, of course, that when a pure hydrocarbon is employed, a correspondingly pure halide is obtained.
Having selected the hydrocarbon in accordance with the desired final product, we chlorinate the hydrocarbon until approximately that amount of chlorine is absorbed which will produce the monochloro compound when that is the desired product, or approximately that amount of chlorine which will produce the dichloro compound when that is the desired product, etc.
In the case of paraflin hydrocarbons having from 18 to 24 carbon atoms per molecule; that is, a material having a melting point of approximately 120 F., about 10 per cent added chlorine will produce substantially the equivalent of the monochloro product. The amount of chlorination may vary between 8 per cent and 12 per cent without being disadvantageous. The percentage of chlorine introduced into the hydrocarbon just described will be approximately 17 per cent when a dichloro product is desired. The amount of chlorine introduced will be less in the case of the high molecular weight, higher melting hydrocarbons, and more in the case of the lower molecular weight, lower melting hydrocarbons, for a given number of chlorine atoms per molecule. The chlorination may be accomplished in any suitable manner. We prefer to heat the hydrocarbon to a temperature at least that of its melting point and pass chlorine gas through the melted hydrocarbon. Agitation increases the efficiency of chlorine absorption but is not essential. The chlorination reaction is exothermic and the heat of reaction is ordinarily ample to maintain the mixture in the liquid state without the addition of other heat. Large quantities of hydrogen chloride gas are evolved which are conducted from the reaction chamber, together with unreacted chlorine. The material being chlorinated is constantly weighed while the chlorination is in progress, in order to determine the extent of chlorination as indicated above. Samples may be removed from time to time, and the specific gravity of these may be determined in order to follow the chlorination process. If desired, chlorine analyses may be conducted on samples of the material being chlorinated. After sufficient chlorine has been introduced, we blow the mixture with air or an inert gas, such as carbon dioxide, until the hydrogen chloride and free chloride, if any, are substantially removed.
As an example of the manufacture of a relatively pure chlorinated hydrocarbon, we describe here the manufacture of a relatively pure monochloro wax which contains approximately 26 carbon atoms per molecule. We started with 723.4 parts of a hydrocarbon wax having a melting point of 120 F. The wax was chlorinated until 72.5 parts by weight of chlorin had been absorbed. The chlorinated wax was air-blown to remove hydrochloric acid and uncombined residual chlorine, and then pressed at 85 F. The unchlorinated wax was reserved for further chlorination. The liquid portion was then dissolved in acetone, 350 parts of crude chloro wax being dissolved in 3,226 parts of acetone. The solution was chilled to minus 18 F. and 185 parts by weight of solid monochloro wax containing 10.3 per cent chlorine was precipitated. Monochlor wax from this paraflin wax contains theoretically 10.0 per cent chlorine. The monochloro wax was normally liquid at room temperatures.
Dichloro waxes and polychloro waxes prepared according to our method are suitable for use in any of the applications described in the prior art, where such dichloro waxes and polychloro waxes are required. Since they contain no unchlorinated wax or lower chlorinated waxes, they are particularly efiicient in these applications and are a distinct improvement over the prior art which used crude chlorination mixtures of approximately the proper chlorine content but which consisted of unchlorinated wax and more highly chlorinated wax.
While chlorine has been referred to above almost exclusively, it is to be understood that any of the halogens are suitable to make halogen derivatives of the parafiin hydrocarbons according to our method. This bromine, iodine, and fluorine may suitably be used to obtain the corresponding bromides, iodides and fluorides. For some purposes to which the halides are to be put, the bromine compounds are much to be desired over the chlorine compounds, since they are considerably more reactive. Where this is the case, we halogenate with bromine, using a halogen carrier, such as halides of antimony, phosphorus, iron, various metals and the like, and separate the brominated mixture into its components as described above in the case of the chlorine compounds. The iodine compounds of the paraffin hydrocarbons may be prepared by direct iodination or by an indirect method. By the indirect method, the above described separation of mono-, di-, and polyhalogen derivatives maybe employed in any step of the process. Thus we may separate a relatively pure mono or dichloro parafiln and convert it to the corresponding iodine compound, or we may convert the crude halogenated mixture into a crude iodlnated mixture and then separate into the various stages of halogenation. Fluorine may be introduced into paraffln hydrocarbons directly or indirectly by analogous methods. For most purposes, however, we prefer to use the chlorine compounds on account of the cheapness and availability of chlorine above all the other halogens.
In preparing sulphur-bearing derivatives of the higher aliphatic hydrocarbons, we treat chemically the relatively pure halogenated hydrocarbons by hydrolytic methods to obtain the corresponding hydroxyl compounds which may be alcohols, glycols, or higher hydroxylated materials according to the number of halogen atoms present in the halogen compound. The derivatives and methods of preparing may be classified as, follows: 117?! r -i 1;
By the action of thionyl chloride on the alcohols.
2. sulfates: By the action of SOzClz on the alcohols or by oxidation of sulfites.
3. Xanthates: By the action of CS2 and caustic alkalies on the alcohols.
, 4. Thiosulfates: From the sulfites and sulfur.
5. Thiophosphates: From the alcohols and thiophosphoryl chloride (PSCh) 6. Thioketones: The alcohols are readily oxidized to ketones which when treated with sulfides of phosphorus yield thioketones.
If our monohalogenated hydrocarbons be hydrolyzed to the corresponding alcohols, these are useful for various sulphur and oiqrgen-bearing derivatives of high molecular weight. Esters of these alcohols with sulphur-containing inorganic and organic acids are particularly interesting. By means of thionyl chloride, the alkyl sulfites of the type, R2803 may be formed. These when treated witirtli' theoretical quantity of elemental sulphur are conve into the corresponding thiosulfates, "RzS2Oa. may be used to pr eir sulfates through the action of sulfuryl chloride, or chlorosulfonic acid. The sulfates may also be prepared by the oxidation of the corresponding sulfites.
In preparing esters of sulfur containing organic acids, we first prepare the alcohol corresponding to our relatively pure monochlor (or monobrom) wax:
Example 1 A mixture of 386 parts of the monochlor wax prepared substantially as described above, 44 parts of caustic soda, and 400 parts of water are agitated thoroughly and heated to 400 F. under pressure for eight hours. The alcohol is separated, washed, and dried.
Example 2 We add 368 parts of this alcohol to 60 parts of boiling thionyl chloride and maintain the temperature of the mixture at 200 F. for five hours. The sulfite is then washed with water and dried.
Thiophosphates of the higher alcohols are produced by the action of thiophosphoryl chloride, PSCla. These products are useful addends to lubricants of all sorts.
Example 3 We reflux a mixture of 1,100 parts of the alcohol of Example 1 with 1'70 parts of thiophosphoryl chloride in 2,000 parts of xylene for eight hours, wash with water, and then dry. On distilling oil the xylene, we obtain our higher alkyl thiophosphate.
When refluxed with caustic alkalies and carbon bisulfides, the higher alcohols give rise to the alkyl xanthates, for example, octadecyl xanthate, pentacosyl xanthate, and the like.
Example 4 We pass chlorine into a commercial grade of octadecane until the weight of 254 parts has increased to 290 parts. The crude chlorination mixture, after air-blowing, is dissolved in acetone, using four times as much acetone by weight as of the chlorination mixture. n cooling to 40 F. most of the unchlorinated hydrocarbon separates and is removed by filtration. The filtrate is cooled to -20 F. and the monochlorinated hydrocarbon removed similarly. It is a liquid at room temperature.
Example 5 We heat at 400 F. in an autoclave, 145 parts of the monchlor octadecane, 22 parts of caustic soda, and 200 parts of water at 350 F. for five hours. The octadecanol is separated, washed, and dried.
Example 6 We dissolve 2'70 parts of octadecanol in 1,000 parts of xylene and heat with 25 parts of sodium until the latter dissolves. To the solution, we add 150 parts of carbon blsulfide and heat the mixture at 300 F. under pressure for four hours. On cooling, we wash out the sodium octadecyl xanthate with water and evaporate the solution to obtain our product.
The high molecular weight alcohols and other oxygen derivatives of paraffin hydrocarbons. such as ketones, aldehydes, esters, amides, and the like, may be converted into compounds in which more or less of the oxygen is replaced by sulphur. Such transformations may be accomplished by heating the oxygen derivative with phosphorus trisulfide or pentasulfide. Some of these reactions proceed without solvent, but in general it is advantageous to use an inert solvent such as benzene or xylene together with good stirring at a suitable reaction temperature. It will be apparent that the solvent must be selected so as to permit of the use of an adequate reaction temperature.
Example 7 We heat 368 parts of the alcohol described in Example 1 to 250 F. and pass dry air through it, absorbing the water from effluent gas until 18 parts have been absorbed. The product is essentially the high molecular weight ketone of the same molecular weight -as the starting material.
Example 8 Into 1,000 parts of xylene, we introduce 366 parts of the ketone of Example 7 and 100 parts of phosphorus trisulfide and boil the mixture for six hours. The solid material is filtered off and the xylene distilled from the residual thioketone.
It is to be understood that any or all of the reactions here described may be carried out under atmospheric or superatmospheric pressure.
It will be seen that we have accomplished the purpose of our invention; namely, to provide relatively pure sulphur-bearing derivatives of high molecular weight parafiin hydrocarbons, each substantially free from other types of sulphur compounds and from unreacted paraffin hydrocarbons.
Having thus described our invention we claim:
1. A method for the synthesis of sulphurbearing derivatives of high molecular weight, including the steps of halogenating paraflinic hydrocarbons whose monochloro derivatives melt lower than the hydrocarbons themselves. separating relatively pure halogenated hydrocarbons from the crude halogenated mixture, hydrolyzing the pure halogenated hydrocarbon with an alkaline reagent and introducing a sulphur-bearing group by reacting the hydroxylated material with a material selected from the group consisting of thiophosphoryl chloride, thionyl chloride and sulphuryl chloride.
2. A method for the synthesis of sulphurbearing derivatives of high molecular weight. including the steps of halogenating paraflinic hydrocarbons whose monochloro derivatives melt lower than the hydrocarbons themselves, separating a relatively pure halogenated hydrocarbon from the crude halogenated mixture, replacing the halogen of said relatively pure halogenated hydrocarbon with hydroxyl groups by means of an alkaline reagent and introducing a sulphurbearing group by reacting the hydroxylated material with thiophosphoryl chloride.
3. A method for the synthesis of sulphurbearing derivatives of high molecular weight, including the steps of halogenating parafiinic hydrocarbons whose monochloro derivatives melt lower than the hydrocarbons themselves, separating a relatively pure halogenated hydrocarbon from the crude halogenated mixture, replacing the halogen of said relatively pure halogenated hydrocarbon with hydroxyl groups by means of an alkaline reagent and introducing a sulphurbearing group by reacting the hydroxylated material with thionyl chloride.
4. A method for the synthesis of sulphurbearing derivatives of high molecular weight, including the steps of halogenating parafiinic hydrocarbons whose monochloro derivatives melt lower than the hydrocarbons themselves, separating a relatively pure halogenated hydrocarbon from the crude halogenated mixture, replacing the halogen of said relatively pure halogenated hydrocarbon with hydroxyl groups by means of an alkaline reagent and introducing a sulphurbearing group by reacting the hydroxylated material with sulphuryl chloride.
LLOYD L. DAVIS. BERT H. LINCOLN. GORDON D. BYRKIT.
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Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2465914A (en) * | 1945-11-30 | 1949-03-29 | Celanese Corp | Stabilized ethyl cellulose |
US2483270A (en) * | 1945-05-30 | 1949-09-27 | Union Oil Co | Lubricating composition |
US2553721A (en) * | 1947-08-20 | 1951-05-22 | Pittsburgh Plate Glass Co | Process of producing sulfite esters |
US2575225A (en) * | 1948-09-29 | 1951-11-13 | Us Rubber Co | Preparation of o-alkyl dichlorothiophosphates |
US2575224A (en) * | 1948-07-17 | 1951-11-13 | Us Rubber Co | Thiophosphates |
US2624750A (en) * | 1948-01-23 | 1953-01-06 | Columbia Southern Chem Corp | Process of producing phosphate ester |
US2819211A (en) * | 1953-02-27 | 1958-01-07 | Exxon Research Engineering Co | Sulfite ester synthetic lubricants |
USRE30797E (en) * | 1977-11-09 | 1981-11-17 | Scott Paper Company | Associated dye salts and method of forming colored indicia therewith |
USRE30803E (en) * | 1977-11-09 | 1981-11-24 | Scott Paper Company | Colorless recording paper |
-
1940
- 1940-09-27 US US358697A patent/US2309829A/en not_active Expired - Lifetime
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2483270A (en) * | 1945-05-30 | 1949-09-27 | Union Oil Co | Lubricating composition |
US2465914A (en) * | 1945-11-30 | 1949-03-29 | Celanese Corp | Stabilized ethyl cellulose |
US2553721A (en) * | 1947-08-20 | 1951-05-22 | Pittsburgh Plate Glass Co | Process of producing sulfite esters |
US2624750A (en) * | 1948-01-23 | 1953-01-06 | Columbia Southern Chem Corp | Process of producing phosphate ester |
US2575224A (en) * | 1948-07-17 | 1951-11-13 | Us Rubber Co | Thiophosphates |
US2575225A (en) * | 1948-09-29 | 1951-11-13 | Us Rubber Co | Preparation of o-alkyl dichlorothiophosphates |
US2819211A (en) * | 1953-02-27 | 1958-01-07 | Exxon Research Engineering Co | Sulfite ester synthetic lubricants |
USRE30797E (en) * | 1977-11-09 | 1981-11-17 | Scott Paper Company | Associated dye salts and method of forming colored indicia therewith |
USRE30803E (en) * | 1977-11-09 | 1981-11-24 | Scott Paper Company | Colorless recording paper |
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