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Green Chemistry
Journal Name
ARTICLE
DOI: 10.1039/C9GC04452C
into a 100 mL-round bottomed flask with a magnetic stirrer under air
To understand why moderate yields were obtained in some
conditions. Then white phosphorus-toluene solution (25 mL, 310 mg
total P4, 0.1 mol/L) was added under air conditions. The flask was
stoppered with a glass stopper and the reaction mixture was stirred
for 7 hours at room temperature. After completion, H2O2 (15 mL)
was added slowly within 10 min, and the mixture was stirred at room
temperature for another 2 hours. Saturated brine (30 mL) was added
into the above reaction mixture. The mixture was extracted by
EtOAc (3×20.0 mL). The combined organic layer was dried over
anhydrous Na2SO4, filtered, and concentrated by rotary evaporation.
The crude reaction mixture was purified by flash chromatography
using petroleum−AcOEt [from 50:1 to 10:1 (v/v)] as the eluent to
give the product 4u (2.61 g, 83%).
transformations but along with the high conversion of P4, the
stability of white phosphorus was monitored. It was found that the
proportion of undestroyed P4 became lower and lower with the
increase of amount of KOH (Scheme 3-6). Attack by hydroxide ion
on the P4 tetrahedron cleaves the first phosphorus-phosphorus bond,
giving the phosphide anion. Repetition of this step breaks all P-P
bonds in P4 under air conditions, leading to the side product
potassium phosphate.48
Based on the above experiments and previous reports,46-48
a
possible reaction mechanism is depicted in Scheme 4. Initially, thiol
1 affords RSK A in the presence of KOH. Meanwhile, the oxidative
coupling of thiol 1 affords disulfide B in the presence of KOH and
air. Subsequent RSK
A attack at a phosphorus atom with
concomitant breakage of one P−P bond results in the opening of the
white phosphorus tetrahedron and formation of a phosphorus-based
anion C. The nucleophilic attack of anion C to disulfide B affords
intermediate D along with the regeneration of RSK A. Further
repetition of these steps results in the formation of
phosphorotrithioite 3. A final oxidation of phosphorotrithioite 3
gives phosphorotrithioate 4.
Conflicts of interest
There are no conflicts to declare.
Acknowledgements
This project was supported by the NSFC (21772163, 21778042) and
NFFTBS (J1310024).
Conclusions
Notes and references
In summary, we have successfully developed the first general and
high yielding synthesis of pharmacologically- and synthetically-
important P(SR)3 and P(O)(SR)3 involving P4, arythiols and
alkylthiols. The use of KOH or K2CO3 as base, DMSO-toluene as
solvent, makes this transformation practical and green. The
operationally simple and mild oxidative reaction shows a broad
scope of substrates and a good functional group tolerance. Moreover,
this method can be easily adapted to large-scale preparation.
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Experimental
Safety note for white phosphorus (P4): White phosphorus is
spontaneously flammable; it should be stored in water or glove box.
On the other hand, white phosphorus is very soluble in toluene.
Synthesis of (n-C10H21S)3P(O) (4w) from 1-decanethiol and white
phosphorus (P4)
KOH (0.26 mmol, 16 mg), n-C10H21SH (210 mg, 1.2 mmol), and
DMSO (0.5 mL) were put into a Schlenk tube with a magnetic stirrer
under air conditions. Then white phosphorus-toluene solution (6.2
mg total P4, 0.5 mL, 0.1 mol/L) was added. The tube was sealed and
the reaction mixture was stirred for 4 hours at room temperature.
After completion, H2O2 (0.5 mL) was added slowly, and the mixture
was stirred at room temperature for another 30 min. The mixture was
extracted by EtOAc (3×10.0 mL). The combined organic layer was
dried over anhydrous Na2SO4, filtered, and concentrated by rotary
evaporation. The crude reaction mixture was purified by flash
chromatography using petroleum−AcOEt [from 50:1 to 10:1 (v/v)]
as the eluent to give the product 4w (95 mg, 84%).
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