Handbook of Solvents - George Wypych - ChemTech - Ventech!

814 Maw-Ling Wang
the organic solvent. The reason is that the concentration of carboxylate ion 54 influences the
concentration of PNO in the organic phase.
Table 13.3.10. Effect of the composition of organic solvent on the PNO-catalyzed
PhCOCl-CH 3COONa reaction in a two-phase medium
Organic phase
kapp×10 -3 min -1 5
at T=
o C 10 o C 18 o C 25 o C 33 o C
CH2Cl2 24.7 32.3 48.5(5.73) b
65.8(12.0) b
CH2Cl2+CCl4 [CCl4]=1.00 M 18.8 26.6 38.3 51.5 72.8
[CCl4]=3.00 M
17.9 26.8
[CCl4]=5.00 M
5.13 9.06 18.1
CH2Cl2+C6H5NO2 [C6H5NO2]=1.00 M 28.0(2.93) b
36.4(6.42) b
62.7(14.6) b
83.0 124
CH2Cl2+CHCl3 [CHCl3]=5.00 M 26.9 37.6 49.0
CH2Cl2+C6H10O [C6H10O]=3.00 M 35.0(4.49) b
57.2(9.38) b
91.4(20.4) b
CHCl3 14.6 19.5 26.7
CCl4 16.2
C6H10O 68.7 106 170
Data obtained from Wang et al. 148 2.00×10 -4 M of PNO, 1.00×10 -2 M of PhCOCl, 0.500 M of CH 3COONa, 18 o C,
1200 rpm, 50 mL of H 2O, 50 mL of organic solvent, b No PNO added; C 6H 10O, cyclohexanone
Figure 13.3.6. Effect of the mole fraction of CCl 4 in the
mixed organic solvent on the k app value in the two-phase
H 2O/(CH 2Cl 2+CCl 4) medium; 1.00×10 -2 M of PhCOCl
0.500 M of CH 3COONa, 2.00×10 -4 M of PNO, 50 mL of
H 2O, 50 mL of organic solvent (CH 2Cl 2+CCl 4), 18 o C.
(Adapted from Ref. [148], by permission.)
In the studies on the inverse
phase-transfer catalytic reaction, Wang, Ou
and Jwo 148 conducted two independent experiments
in order to evaluate the effect of
polarity of the organic phase on the reaction.
In the first experiment, a relatively inert
organic substances such as C 6H 5CH 2CN,
C 6H 5CN, C 6H 5N(Et) 2, C 6H 5NO 2,
CH 3COOC 2H 5 or C 3H 7COOC 2H 5 were individually
added to the organic phase
(CH 2Cl 2) as the mixed organic solvent in
the two-phase reaction system. The reactions
of these compounds with PhCOCl or
PNO were negligibly slow compared to the
reaction of PhCOCl and PNO. The results
are given in Tables 13.3.11 and 13.3.12, respectively.
It is shown that k app increased
with added inert substance of high polarity,