반응 #2459

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Diethyl chlorothiophosphate

ammonia

tetrahydrofuran

sulphuric acid

→

tetraethyl thioimidodiphosphate

용매

dichloromethane

반응 조건

후처리

1. 1
   여과The mixture was filtered
2. 2
   기타to remove
3. 3
   기타precipitated ammonium chloride
4. 4
   농축concentrated by distillation of the solvent under reduced pressure to a yellow oil (diethyl thiophosphoramide, 21.0 g, 31P NMR in CDCl3, singlet, 67.4 ppm downfield of H3PO4)
5. 5
   기타Without further purification
6. 6
   workup.DISSOLUTIONthis amide (8.5 g) was redissolved in tetrahydrofuran (250 cm3)
7. 7
   workup.ADDITIONsodium hydride (13.2 g of a 20% suspension in toluene) was added
8. 8
   workup.STIRRINGwith stirring
9. 9
   workup.ADDITIONdiethyl chlorothiophosphate (9.5 g) was added dropwise during 15 min
10. 10
    workup.STIRRINGThe mixture was stirred
11. 11
    온도and then cooled
12. 12
    여과filtered
13. 13
    workup.DISTILLATIONThe solvent was distilled under reduced pressure
14. 14
    기타leaving a yellow oil which
15. 15
    기타The organic phase was separated
16. 16
    건조dried with magnesium sulphate
17. 17
    여과filtered
18. 18
    농축concentrated by distillation of solvent under reduced pressure

실험 절차

Diethyl chlorothiophosphate (25.04 g, supplied by Aldrich Chemical Company Ltd.) was added dropwise with stirring to a saturated solution of ammonia in tetrahydrofuran (250 cm3). Stirring was continued for two hr. The mixture was filtered to remove precipitated ammonium chloride and then concentrated by distillation of the solvent under reduced pressure to a yellow oil (diethyl thiophosphoramide, 21.0 g, 31P NMR in CDCl3, singlet, 67.4 ppm downfield of H3PO4). Without further purification, this amide (8.5 g) was redissolved in tetrahydrofuran (250 cm3) and sodium hydride (13.2 g of a 20% suspension in toluene) was added with stirring. When hydrogen ceased to be evolved, diethyl chlorothiophosphate (9.5 g) was added dropwise during 15 min. The mixture was stirred and heated at 65° C. for 2 hr. and then cooled and filtered. The solvent was distilled under reduced pressure leaving a yellow oil which was dissolved in dichloromethane (250 cm3) and stirred with dilute sulphuric acid (1 molar to ensure that the pH of the suspension was less than pH 2). The organic phase was separated, dried with magnesium sulphate, filtered, and concentrated by distillation of solvent under reduced pressure yielding tetraethyl thioimidodiphosphate (11.2 g. 31P NMR in CDCl3, singlet, 56.4 ppm downfield of H3PO4). The purity was determined by titration of a sample dissolved in 50% tetrahydrofuran-water with 0.1M aqueous sodium hydroxide solution for the acidic (NH or SH) proton, which was 50% neutralised at pH 6.1. By this method the purity was found to be 77% of theoretical based on molecular weight 321. The compound of Formula I in which R1 =R2 =R3 =R4 =ethoxy was examined as an extractant for zinc by Tests 1 and 2, with the results listed in Tables 1 and 2, which show that it is a weak extractant for zinc with high selectivity over iron.

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