GB744484A - Production of dialkylamidophosphoryl halides, hexa-alkyl phosphorylamides and octa-alkyl pyrophosphorylamides - Google Patents
Production of dialkylamidophosphoryl halides, hexa-alkyl phosphorylamides and octa-alkyl pyrophosphorylamidesInfo
- Publication number
- GB744484A GB744484A GB573353A GB573353A GB744484A GB 744484 A GB744484 A GB 744484A GB 573353 A GB573353 A GB 573353A GB 573353 A GB573353 A GB 573353A GB 744484 A GB744484 A GB 744484A
- Authority
- GB
- United Kingdom
- Prior art keywords
- phosphoryl
- halide
- acid acceptor
- thiophosphoryl
- chloride
- 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
Links
- 150000004820 halides Chemical class 0.000 title abstract 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract 16
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 abstract 12
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 abstract 10
- 239000000370 acceptor Substances 0.000 abstract 10
- 239000002253 acid Substances 0.000 abstract 9
- -1 phosphoryl halides Chemical class 0.000 abstract 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 abstract 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 abstract 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 abstract 6
- 239000000203 mixture Substances 0.000 abstract 6
- 229910000029 sodium carbonate Inorganic materials 0.000 abstract 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 abstract 3
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 abstract 3
- 125000000217 alkyl group Chemical group 0.000 abstract 3
- 125000005265 dialkylamine group Chemical group 0.000 abstract 3
- 125000005843 halogen group Chemical group 0.000 abstract 3
- 229910000039 hydrogen halide Inorganic materials 0.000 abstract 3
- 239000012433 hydrogen halide Substances 0.000 abstract 3
- 238000000034 method Methods 0.000 abstract 3
- 239000011541 reaction mixture Substances 0.000 abstract 3
- WQYSXVGEZYESBR-UHFFFAOYSA-N thiophosphoryl chloride Chemical compound ClP(Cl)(Cl)=S WQYSXVGEZYESBR-UHFFFAOYSA-N 0.000 abstract 3
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 abstract 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 abstract 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract 2
- 239000005864 Sulphur Chemical group 0.000 abstract 2
- 150000001412 amines Chemical class 0.000 abstract 2
- 239000007864 aqueous solution Substances 0.000 abstract 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract 2
- 229910052751 metal Inorganic materials 0.000 abstract 2
- 239000002184 metal Substances 0.000 abstract 2
- 150000007522 mineralic acids Chemical class 0.000 abstract 2
- 239000001301 oxygen Substances 0.000 abstract 2
- 229910052760 oxygen Inorganic materials 0.000 abstract 2
- LFGREXWGYUGZLY-UHFFFAOYSA-N phosphoryl Chemical group [P]=O LFGREXWGYUGZLY-UHFFFAOYSA-N 0.000 abstract 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 abstract 2
- 150000003839 salts Chemical class 0.000 abstract 2
- 239000000243 solution Substances 0.000 abstract 2
- JITSWUFGPFIMFG-UHFFFAOYSA-N 1,1,2,2,4-pentachlorobutane Chemical compound ClCCC(Cl)(Cl)C(Cl)Cl JITSWUFGPFIMFG-UHFFFAOYSA-N 0.000 abstract 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 abstract 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 abstract 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 abstract 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 abstract 1
- 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 abstract 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract 1
- 150000001408 amides Chemical class 0.000 abstract 1
- 239000007900 aqueous suspension Substances 0.000 abstract 1
- 229910052788 barium Inorganic materials 0.000 abstract 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 abstract 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 abstract 1
- 229910052794 bromium Inorganic materials 0.000 abstract 1
- 229910052791 calcium Inorganic materials 0.000 abstract 1
- 239000011575 calcium Substances 0.000 abstract 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 abstract 1
- 239000000920 calcium hydroxide Substances 0.000 abstract 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 abstract 1
- 239000000460 chlorine Substances 0.000 abstract 1
- 229910052801 chlorine Inorganic materials 0.000 abstract 1
- 150000001805 chlorine compounds Chemical class 0.000 abstract 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 abstract 1
- 239000003085 diluting agent Substances 0.000 abstract 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 abstract 1
- LIWAQLJGPBVORC-UHFFFAOYSA-N ethylmethylamine Chemical class CCNC LIWAQLJGPBVORC-UHFFFAOYSA-N 0.000 abstract 1
- 229910052731 fluorine Inorganic materials 0.000 abstract 1
- 239000011737 fluorine Substances 0.000 abstract 1
- 150000008282 halocarbons Chemical class 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract 1
- 229910052740 iodine Inorganic materials 0.000 abstract 1
- 239000011630 iodine Substances 0.000 abstract 1
- 239000003350 kerosene Substances 0.000 abstract 1
- 229910052744 lithium Inorganic materials 0.000 abstract 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical class [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 abstract 1
- 235000012254 magnesium hydroxide Nutrition 0.000 abstract 1
- 239000003960 organic solvent Substances 0.000 abstract 1
- 125000001863 phosphorothioyl group Chemical group *P(*)(*)=S 0.000 abstract 1
- 229910000027 potassium carbonate Inorganic materials 0.000 abstract 1
- 150000003335 secondary amines Chemical class 0.000 abstract 1
- 239000011734 sodium Substances 0.000 abstract 1
- 229910052708 sodium Inorganic materials 0.000 abstract 1
- 239000001488 sodium phosphate Substances 0.000 abstract 1
- 239000007787 solid Substances 0.000 abstract 1
- 239000002904 solvent Substances 0.000 abstract 1
- 229910052712 strontium Inorganic materials 0.000 abstract 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 abstract 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 abstract 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 abstract 1
- 235000019801 trisodium phosphate Nutrition 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract 1
- 229910052727 yttrium Inorganic materials 0.000 abstract 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 abstract 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
- C07F9/22—Amides of acids of phosphorus
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
Abstract
Dialkylamido phosphoryl halides and hexaalkyl phosphoryl amides having the general formula <FORM:0744484/IV(a)/1> in which R1 and R2 are both alkyl groups, X is oxygen or sulphur, Y is a halogen atom or a group having the general formula -NR3R4, and Z is a halogen atom or a group having the general formula -NR5R6, R3, R4, R5 and R6 being alkyl groups, are obtained by treating a phosphoryl halide or a thiophosphoryl halide with at least a stoichiometric proportion of a dialkylamine for each dialkylamido group desired in the product and either simultaneously or subsequently introducing an inorganic acid acceptor into the reaction mixture in an amount at least sufficient to combine with the hydrogen halide generated by the reaction. The invention also provides a process of producing an octa-alkyl pyrophosphorylamide having the general formula <FORM:0744484/IV(a)/2> in which R1, R2, R3 and R4 are alkyl groups and each X is oxygen or sulphur by treating a phosphoryl halide or a thiophosphoryl halide with substantially 2 mols. of a dialkyl amine for each mol. of halide and either simultaneously or subsequently introducing at least three equivalents of an inorganic acid acceptor into the reaction mixture. The acid acceptor may be a hydroxide or a salt of a metal which is decomposed by a hydrogen halide, e.g. a salt of a weak or easily displaced acid of a metal above yttrium in the electromotive series. The acid acceptor should be present in an amount at least equivalent to the hydrogen halide. Specified acid acceptors are sodium carbonate, potassium carbonate, trisodium phosphate, and lithium, barium, calcium, sodium, strontium, and magnesium hydroxides, and mixtures thereof. The acid acceptor may be incorporated into the reaction mixture in solid form or in aqueous solution or suspension but excessive quantities of water should be avoided. The reaction is preferably carried out in the presence of an inert organic solvent or diluent, e.g. a halogenated hydrocarbon such as trichloroethylene, ethylene dichloride, and chloroform, or toluene, kerosene, or benzene. It is preferred to add the amine to the phosphoryl halide gradually and then add the acid acceptor to the mixture of amine and phosphoryl halide. The preferred dialkylamines are dimethyl-, diethyl-, dipropyl-, diisopropyl-, dibutyl-, and methylethyl-amines. In examples: (1) bis (dimethylamido) phosphoryl chloride is obtained by adding dimethylamine to phosphoryl chloride in the presence of trichloroethylene and then adding either calcium hydroxide followed by aqueous sodium hydroxide, or aqueous potassium hydroxide; (2) bisdimethyl (and bisdiethyl-)a midophosphoryl chlorides respectively are obtained from the corresponding secondary amine as in (1) potassium hydroxide being added as acid acceptor and ethylene dichloride being employed as solvent; (3) as in (1) except that sodium hydroxide solution is used as acid acceptor; (4) bis (dimethylamido) thiophosphoryl chloride is obtained by passing gaseous dimethylamine into a mixture of thiophosphoryl chloride and chloroform and then adding aqueous sodium hydroxide; (5) dimethylamido thiophosphoryl dichloride is obtained by passing gaseous dimethylamine into a mixture of thiophosphoryl chloride and trichloroethylene and then adding finely-divided sodium carbonate; (6) dimethylamido phosphoryl dichloride is obtained by a procedure similar to (5) except that phosphoryl chloride and ethylene dichloride are used; (7) bis (dimethylamido) phosphoryl chloride is obtained by a procedure similar to (1) except that finely-divided sodium carbonate is added as acid acceptor; (8) octamethylpyrophosphoryl amide is obtained by passing gaseous dimethyl amine into a mixture of phosphoryl chloride and trichloroethylene and then adding either sodium carbonate or sodium hyroxide solution followed by flake sodium hydroxide; (9) hexamethylphosphorylamide is obtained by adding dimethyl-amine to a mixture of phosphoryl chloride and chloroform and then adding an aqueous solution of sodium hydroxide. The halogen atom in the phosphoryl or thiophosphoryl halide is preferably chlorine but may also be bromine, iodine or fluorine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB573353A GB744484A (en) | 1953-03-02 | 1953-03-02 | Production of dialkylamidophosphoryl halides, hexa-alkyl phosphorylamides and octa-alkyl pyrophosphorylamides |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB573353A GB744484A (en) | 1953-03-02 | 1953-03-02 | Production of dialkylamidophosphoryl halides, hexa-alkyl phosphorylamides and octa-alkyl pyrophosphorylamides |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| GB744484A true GB744484A (en) | 1956-02-08 |
Family
ID=9801612
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB573353A Expired GB744484A (en) | 1953-03-02 | 1953-03-02 | Production of dialkylamidophosphoryl halides, hexa-alkyl phosphorylamides and octa-alkyl pyrophosphorylamides |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB744484A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4646107A (en) * | 1983-05-21 | 1987-02-24 | Pilot Man-Nen Hitsu Kabushiki Kaisha | XY plotter apparatus |
-
1953
- 1953-03-02 GB GB573353A patent/GB744484A/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4646107A (en) * | 1983-05-21 | 1987-02-24 | Pilot Man-Nen Hitsu Kabushiki Kaisha | XY plotter apparatus |
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