Potassium di-tert-butyl phosphate CAS 33494-80-3
Potassium di-tert-butyl phosphate Basic information
| Product Name: | Potassium di-tert-butyl phosphate |
| Synonyms: | DI-TERT-BUTYLPHOSPHATE, POTASSIUM SALT;DI-TERTIARYBUTYL PHOSPHATE (POTASSIUM SALT);Di-t-butyl phosphate, potassium salt;Nsc264063;Potassium di-t-butylphosphate, min. 91% (contains <5% water);Di-tert-butyl phosphate;POTASSIUM DI-TERT-BUTYLPHOSPHATE;bis(tert-butoxy)phosphinic acid potassium hydride |
| CAS: | 33494-80-3 |
| MF: | C8H18KO4P |
| MW: | 248.3 |
| EINECS: | 619-702-9 |
| Product Categories: | |
| Mol File: | 33494-80-3.mol |
Potassium di-tert-butyl phosphate Chemical Properties
| Melting point | 247-252°C |
| storage temp. | 2-8°C |
| form | Powder |
| color | white |
| InChI | InChI=1S/C8H19O4P.K/c1-7(2,3)11-13(9,10)12-8(4,5)6;/h1-6H3,(H,9,10);/q;+1/p-1 |
| InChIKey | ZSWXMOQFFWMZQH-UHFFFAOYSA-M |
| SMILES | [K+].P([O-])(OC(C)(C)C)(OC(C)(C)C)=O |
| CAS DataBase Reference | 33494-80-3 |
Safety Information
| Hazard Codes | Xi |
| Risk Statements | 36/37/38 |
| Safety Statements | 26 |
| WGK Germany | 3 |
| TSCA | No |
| HS Code | 2919900090 |
| Storage Class | 11 - Combustible Solids |
| Hazard Classifications | Eye Irrit. 2 Skin Irrit. 2 STOT SE 3 |
| Uses | Di-tert-butylphosphate Potassium Salt is a catalyst used in organic synthesis. Also used in the preparation of HIV attachment inhibitor BMS-663068. |
| Application | Utilized as an intermediate to prepare N-phosphonooxymethyl prodrugs, which increase bioavailability, and to prepare Nasicon-type phosphates (i.e., KTi2(PO4)3) used in fast ion conductors with low thermal expansion ceramics.appl |
| Preparation | Potassium di-tert-butyl phosphate synthesis: Di-tert-butyl phosphite (40.36 mmol) was combined with potassium bicarbonate (24.22 mmol) in 35 ml of water. The solution was stirred in an ice bath and potassium permanganate (28.25 mmole) was added in three equal portions over a period of one hour. The reaction was then allowed to continue for another half hour at room temperature. Decolorizing carbon (600 mg) was then incorporated as the reaction was heated to 60 °C for 15 min. The reaction was then vacuum filtered to remove solid magnesium dioxide. The solid was washed several times with water. The filtrate was then combined with one gram of decolorizing carbon and heated at 60°C for another twenty minutes. The solution was filtered again to give a colorless solution, which was then evaporated in vacuo to give the crude potassium di-tert-butyl phosphate salt. |
| Flammability and Explosibility | Non flammable |
| reaction suitability | reaction type: Buchwald-Hartwig Cross Coupling Reaction reaction type: Heck Reaction reaction type: Hiyama Coupling reaction type: Negishi Coupling reaction type: Sonogashira Coupling reaction type: Stille Coupling reaction type: Suzuki-Miyaura Coupling reagent type: ligand |
| Synthesis | 13086-84-5 33494-80-3 General procedure for the synthesis of the potassium salt of di-tert-butyl phosphate from di-tert-butyl phosphite:1. di-tert-butyl phosphite (40.36 mmol) was mixed with potassium bicarbonate (24.22 mmol) in 35 mL of water.2. the mixed solution was placed in an ice bath with stirring and potassium permanganate (28.25 mmol) was added in three equal portions over a period of 1 hour.3. The reaction continues to be stirred at room temperature for 30 minutes.4. Decolorized carbon (600 mg) was added and the reaction mixture was heated to 60 °C and maintained for 15 min.5. The reaction mixture was vacuum filtered to remove the solid manganese dioxide. 6.6. The solid was washed several times with water.7. The filtrate was combined with 1 g of decolorized carbon and heated at 60 °C for 20 min.8. The filtrate was filtered again to give a colorless solution followed by vacuum evaporation to give the crude di-tert-butyl potassium phosphate salt.9. The crude potassium salt of di-tert-butyl phosphate (5 g, 20.14 mmol) was dissolved in methanol (15 g).10. A slight excess of concentrated hydrochloric acid was slowly added to the solution at 0 °C while maintaining effective stirring.11. After addition of hydrochloric acid, potassium chloride precipitated, filtered and washed with methanol.12. An equimolar amount of tetramethylammonium hydroxide (3.65 g, 20.14 mmol) was added to the mother liquor while the reaction was kept cool and effectively stirred in a salt/ice bath.13. The resulting clarified solution was placed under reduced pressure to give the crude product.14. Tetramethylammonium di-tert-butyl phosphate was dissolved in refluxed dimethoxyethane, chloroiodomethane (4.3 g, 24.16 mmol) was added and stirred for 1-2 hours.15. The reaction mixture was filtered and the filtrate was concentrated under reduced pressure to give a solution of dimethoxyethane.16. The chloromethyl di-tert-butyl phosphate (12-16%) from this solution was used directly in the next step in the synthesis of 4-(5-(2-(2-(3,5-bis(trifluoromethyl)phenyl)-N,2-dimethylpropanamido)-4-(o-tolyl)pyridin-2-yl)-1-methyl-1-((phosphonoyloxy)methyl)piperazin-1-ium without further purification (60% yield).Characterization data:1H NMR (CD3OD, 300 MHz) δ 1.51 (s, 12H), 5.63 (d, 2H, J = 14.8 Hz).31P NMR (CD3OD, 300 MHz) δ -11.3 (s, 1P). |
| References | [1] Patent: EP1051181, 2004, B1. Location in patent: Page/Page column 15 [2] Patent: US8426450, 2013, B1. Location in patent: Page/Page column 32; 33 [3] Patent: US9403772, 2016, B2. Location in patent: Page/Page column 37 [4] Patent: JP2015/17121, 2015, A. Location in patent: Paragraph 0179-0181 |
Potassium di-tert-butyl phosphate Preparation Products And Raw materials
| Raw materials | DI-TERT-BUTYL PHOSPHITE-->Potassium bicarbonate-->Decolorizing charcoal-->Potassium permanganate |
