Our beeloved Chemistry Lover Diafrag of HyperLab recently scanned and uploaded that very article to his site http://chemlover.narod.ru (http://chemlover.narod.ru)
. There are some points in it that could bee helpful to the future generations ;) :
1) The optimal rxn time (they say) is 50 C, but it is absolutely uncrucial - like 25 C is good (173 hours for MeOH) - 100% yield.
2) Lower alcohols are converted into TAlkP's - although EtOH gives about 33% triethylphosphite as a byproduct (again, at RT, 246 hrs).
3) Higher alcohols are converted to dialkylphosphates - but they react further to TAlkP's if the water formed is azeotropically removed. Again, some TAlkP-ites are formed as byproduct.
4) There is actually a table summarizing the rxn kynetics at RT for different alcohols - i am too as-busy-as-a-bee :) to type it in, read it in the original at http://chemlover.narod.ru/articles/article5.djv (http://chemlover.narod.ru/articles/article5.djv)
5) They state the rxn equation to bee:
NaOH2PO + 4 CuCl2 + 3 ROH ----> 4 CuCl + NaCl + 3 HCl + H2O + (RO)3PO4
6) BUT you know what - "....cuprous chloride formed is re-oxidized by air to cupric chloride..." so they actually perform the rxn (at RT and long time) in ambient atmosphere , with molar concentrations of the reagents being actually 1,14 g/mole NaH2PO2 and 0,74 g/mole CuCl2.
It also suggest a possible explanation, as well as a possible tremendous improvement for Half-A-Pint's DMS synthesis (BTW, Uemura, earlier in this thread you say that your attempts to make DMS failed - what did you mean? Did you try the CuCl2 method?)
7) Finally, cupric bromide cannot bee substituted for chloride in this reaction.
Antoncho
Thank you! I have reinserted those pixtures into the appropriate post and added Uemuras writeup to the document at https://www.thevespiary.org/rhodium/Rhodium/chemistry/me3po4.html (https://www.thevespiary.org/rhodium/Rhodium/chemistry/me3po4.html)
Acid Catalysis of Phenol Etherifications With Trialkylphosphates
Patent US2683784 (http://l2.espacenet.com/dips/viewer?PN=US2683784&CY=gb&LG=en&DB=EPD)
Example 2
Seventy-one grams of phenol (0.75 mole), 40 grams of trimethylphosphate (0.286 mole) and 0.5 gram of p-toluene sulfonic acid were heated together. The reaction was proceeding slowly so 1.0 gram more p-toluene sulfonic acid was added and the reaction proceeded rapidly. The anisole was distilled out of the reaction mixture through a short column; B. P. 155-158o C., yield 75 g. (92 per cent).