Pergamon

Chemical Engineering Science, Vol. 50, No. 6, pp, 943 949, 1995 Copyright 1995 Elsevier Science Ltd Printed in Great Britain, All rights reserved 0009-2509/95 $9.50 + 0.00

0009-2509(94)00493-5

SYNTHESIS OF HIPPURIC ACID WITH INVERSE PHASE TRANSFER CATALYST IN A HETEROGENEOUS L I Q U I D - L I Q U I D REACTION SYSTEM
S. ASAI, t H. NAKAMURA, W. OKADA and M. YAMADA Department of Chemical Engineering, University of Osaka Prefecture, Sakai, Osaka 593, Japan
(Received 13 December 1993; accepted in revised form 14 October 1994)
Abstract--The synthesis of hippuric acid from benzoyl chloride and glycine in the presence of 4-

dimethylaminopyridineas an inverse phase transfer catalyst was carried out in heterogeneous liquid-liquid reaction system using an agitated vesselwith a fiat interface.By this synthetic technique, the hippuric acid of high product yield could be obtained without the addition of alkali. The observed overall reaction rates were proportional to the interfacial concentration of salt, 1-benzoyl-4-dimethylaminopyridinium chloride in the aqueous phase, which is formed by the reaction between benzoyl chloride and 4-dimethylaminopyridine in the organic phase. The overall reaction rates could be reasonably explained by the proposed theoretical model for the inverse phase transfer catalysis considering the mass transfer resistance of relevant reaction species. The reaction rate constant evaluated by fitting the rate data to the model prediction was 6.50 m3/(kmol s) at 303 K. 1. INTRODUCTION Phase transfer catalyst such as a quaternary ammonium salt or a crown ether is well known to accelerate many reactions under the mild conditions, where the reactions hardly take place in the absence of the catalyst due to the sparing mutual solubility (Starks and Liotta, 1978; Dehmlow and Dehmlow, 1983; Keller, 1986; Asai etal., 1992). Recently, Mathias and Vaidya (1986) has reported that 4dimethylaminopyridine which is a kind of highly active acylation catalyst undergoing an inverse phase transfer catalysis. Later, Fife et al. (1987), Zeldin et al. (1989) and Rubinsztajn et al. (1990) also demonstrated that silanes and siloxanes functionalized with 4(dialkylamino)pyridine moieties are the other kinds of acylation catalyst undergoing an inverse phase transfer catalysis. Since these catalysts can make the reactant in the organic phase move into the aqueous phase, the use will be noted as a technique of new synthetic reaction or enzymatic processes using the slightly soluble organic reactant in water. However, the reaction examples for inverse phase transfer catalysis is rare. Mathias and Vaidya carried out the reaction of DL-alanine with decanoyl chloride or p-chlorobenzoyl chloride using 4dimethylaminopyridine (DMAP) as an inverse phase transfer catalyst, and demonstrated a cycle scheme of inverse phase transfer catalysis. From the qualitative experiment, they described that the interfacial mass transfer of reaction species is the rate-limiting step, but they did not make the quantitative analysis in view of the chemical reaction engineering. In the present work, we chose the synthetic reaction of hippuric acid, that is, benzoyl glycine from benzoyl chloride and glycine by using DMAP as a reaction ~Author to whom correspondence should be addressed. example of the inverse phase transfer catalysis, and made the analysis allowing for the effect of mass transfer on overall reaction rate. Hippuric acid is the precursor for the synthesis of the aromatic amino acids such as phenylalanine and tryptophan etc. and the raw material of azlactone dyes. In the synthesis of hippuric acid by the conventional Schotten-Baumann method using a concentrated alkaline solution, the very low solubility of benzoyl chloride in the aqueous phase and the loss of benzoyl chloride by the alkaline hydrolysis were disadvantageous. However, the inverse phase transfer catalyst can enhance the solubility of benzoyl chloride in water. Thus, the significantly enhanced overall reaction rate can be expected. In addition, the inverse phase transfer catalyst can promote the reaction even in the absence of alkali, which causes the hydrolysis of benzoyl chloride. In this work, in the first place, the equilibrium constant of formation of salt, 1-benzoyl-4-dimethylaminopyridinium chloride (BDPC), from DMAP and benzoyl chloride in the organic phase, and the distribution coefficients of DMAP and BDPC between aqueous and organic phases were measured. Next, the synthesis of hippuric acid was carried out in a heterogeneous liquid-liquid reaction system by varying the concentrations of DMAP and benzoyl chloride in the organic phase and of glycine in the aqueous phase. Furthermore, the measured overall reaction rates were analyzed by comparing them with the theoretical predictions considering the mass transfer resistance of relevant reaction species.

2. EXPERIMENTAL

1,2-Dichloroethane was used as an organic solvent. The equilibrium constant of the formation of BDPC 943

944

S. ASAI et al.

in 1,2-dichloroethane was measured at 303 K using the system of 0.005-0.02kmol/m 3 DMAP and 0.085-0.34 kmol/m 3 benzoyl chloride. After the solution was vigorously shaken for 1 h and permitted to stand, the concentrations of DMAP, BDPC and benzoyl chloride were analyzed by high performance liquid chromatography (HPLC). The measurement of the distribution equilibrium of DMAP and BDPC were carried out using a shaker. The volume of 2.0 x 10- s m 3 of the organic 1,2-dichloroethane solutions containing 0.0050.02 kmol/m 3 DMAP and 0.085-0.34 kmol/m 3 benzoyl chloride were vigorously shaken at 303 K with the same volume of water containing 0-0.8 kmol/m 3 glycine (Gly) for 1 h. After attainment of equilibrium, the concentrations of DMAP and BDPC in the aqueous and organic phases were analyzed by HPLC and their distribution coefficients were determined. In the main experiments, the same agitated vessel with a fiat interface as that used in the previous work (Asai et al., 1983) was used as a reactor. The internal diameter of the agitated vessel was 0.080 m, yielding an interfacial area of 5.04 x 10 - 3 m 2 and a liquid volume of 4.02 x 10 -4 m 3 for each phase. The organic phase consisted of 0.085-0.34kmol/m 3 benzoyl chloride diluted with 1,2-dichloroethane and the aqueous phase consisted of the solutions containing 0.01-0.10kmol/m 3 DMAP and 0.1-0.8kmol/m 3 glycine. For comparison, the experiments for the systems containing 0.2-3.0 kmol/m 3 NaOH instead of DMAP were also carried out in some runs. Samples of 1 . 0 10 - 6 m 3 were taken from the aqueous and organic phases at intervals of l0 min. The concentrations of hippuric acid in the aqueous phase, of DMAP and BDPC in the two phases and of benzyol chloride in the organic phase were measured by HPLC. The overall reaction rates were evaluated from the concentration variations of hippuric acid with time in the initial period. The experiments were carried out at the temperature of 303 K and at agitation speeds of

2.5 s- 1 for each phase, yielding kL and kL of around 1.0 x 10 -5 and 1.6 x l0 -s m/s, respectively.

3. REACTION M O D E L AND ANALYTICAL P R O C E D U R E

The reaction model for the present heterogeneous reaction system is illustrated in Fig. 1. First, the inverse phase transfer catalyst DMAP dissolved in the aqueous phase moves to the organic phase. It is assumed that DMAP in the organic phase reacts with benzoyl chloride instantaneously and reversibly, according to reaction (b), to form the salt BDPC. The formed BDPC moves into the aqueous phase and reacts with glycine existing there originally, according to reaction (a). The main reaction (a) in the aqueous phase can be regarded as a pseudo first-order reaction with respect to BDPC because the concentration of glycine is much larger than equilibrium concentration of BDPC. Furthermore, this reaction is assumed to be irreversible. The product DMAP transfers to the organic phase again and this catalytic reaction cycle is repeated. The differential equations, based on the film theory for the relevant species in the aqueous phase, can be expressed as d 2[DMAP] D1 dz 2 where d 2[BDPC] -D E dz 2 - k ' [BDPC] (1)

k'= k [Gly]b

(2)

[Gly]b is the bulk concentration of glycine in the aqueous phase. For the species in the organic phase, the diffusion equations can be expressed as _ d 2 [DMAP] Dl dz 2 -~, d 2 [Bz-C1] D2d 2 [BDPC] dz2 "=-1)3 ~Z2

= k, [DMAP] [Bz-CI] - k_, [BDPC]

(3)

CHa.N.-CHa CH3.N..-CH3 NHCH2COOH aqueous phase

+ C~ + HCl ,,

NH2CH2COOH + (Glycine)

CI-

(a)

(DMAP) (Hippuric acid) interface 0

N1

(BDPC)

CHa
/

CHa"N/CH3 organic phase

(DMAP)

COCl

k~ ~,

-"'

CH3 N r ~ ClL,.~-~p+

(b)

(Benzoylchloride) Fig. 1. Reaction model.

(BDPC)

Synthesis of hippuric acid with inverse phase transfer catalyst where [Bz-C1] refers to benzoyl chloride concentration in the organic phase. The boundary conditions for these equations are:

945

[Bz-CI] i = _lkL3 \ ( m 2 t a n h k L 2 T ? kL2) [BDPC], + ~[~]~, + [Bz-Cl]b

(lO)

z=6(>0):
[DMAP] = [DMAP]b, [BDPC] = 0
z=0: [ D M A P ] i - (ml kcl -- kL,) ((kL2 -- mEkm)[BDPC]i - kL2[BDPC]b +
1

[DMAP] = [DMAP],, [BDPC] = [BDPC], [DMAP] = [DMAP],, [BDPC] = [BDPC],

[Bz-Ci] = [Bz-C1]

kL1 [DMAP]b
(11)

(4)
where

+ EL1 [DMAP]b)

z=3(>0):
[ D M A P ] = [DMAP]b, [BDPC] = [BDPC]b [Bz-C1] = [Bz-CI] b where the condition of [BDPC] = 0 means that the irreversible reaction (a) completes in the bulk of aqueous phase. Mass balances at the interface (z = 0) result in:

k~2/kL2 = x/k[Oly]bD2/kL2
ktj =

(12) (13)

D;/6,

EL; = D/6.

Nl = Dl d[DMAP] ~=o = -- D1 d[DMAP]

dz dz

: =o

+
N2
= -

D3 d[Bz-Cl] ~=o

dz

(5)

The value of 7 and the inteffacial concentration [BDPC]~ of BDPC in the aqueous phase can be evaluated by comparing the observed mass transfer rates N2 with solution of the simultaneous equations (7)-(11). Furthermore, as will be discussed later it may be found from the observed concentrations of relevant species and the distribution relationship that the first and third terms of the right-hand side of eq. (10) are much larger than the second one, and the third term of the right-hand side in eq. (11) are substantially larger than the others. Then one obtains the following approximate expression for the interfacial concentration of BDPC in the aqueous phase [BDPC]i =

D2d[BDPC]I = D2 d [BDPC] dz Iz=o ~zz :=o (6)

m2KkL1 [Bz-C1]b [DMAP]b glkcl (mEkL2? mlkLl--kLl--~-L3 \t~nhy

kL2)[DMAP]b (14) The value of ? can be estimated by comparing the observed mass transfer rates N 2 with eqs (9) and (14). Thus, one can determine the reaction rate constant k from the evaluated value of 7 by means of eq. (12).
4. PHYSICAL PROPERTIES

D3 dEBz'Cl] :=o" + dz

The interfaciai mass transfer of benzoyl chloride and glycine may be neglected, because they can be regarded as insoluble to aqueous and organic phases, respectively. From the distribution equilibria of D M A P and BDPC: [ D M A P ] ~ =ml [ D M A P ] i, [BDPC] i = m2[BDPC] i. (7) The equilibrium relationship of reaction (b) in the organic phase may be expected to hold at any place, by the assumption of the instantaneous reversible reaction:

kl
K=~-~

[BDPC]i
[DMAP],[Bz-CI],

[BDPC]b
[DMAP]b[Bz-C1]b

(8)
Solving eqs (1)-(7), the following equations are derived. N2 = ~ km [BDPC] i (9)

The densities, the viscosities and the interfacial tensions of the solutions used in all the experiments were measured in a similar manner to those in the previous paper (Asai et al., 1992). The diffusivities of D M A P in the aqueous and organic phases, and of benzoyl chloride in the organic phase were measured with a conventional diaphragm cell. The observed diffusivities of D M A P in the aqueous and organic phases and of benzoyl chloride in the organic phase were found to be 7.19x10 -1, 1.20x 10 -9 and 1.23 x 10 -9 m2/s, respectively, at 303 K. They agreed with the predicted values from the correlation of Wilke and Chang (1955) with an error of less than 10%. The diffusivities of BDPC in the aqueous and organic phases could not be measured because the pure reagent of BDPC was not available Thus, they were predicted by using the correlation of

C E S50:6-D

946

S. ASAIet al. BDPC was not influenced by the concentration of benzoyl chloride, but the distribution of DMAP into the aqueous phase increased with the concentration of benzoyl chloride. From the slopes of the straight lines for each concentration of benzoyl chloride in Fig. 3, the distribution coefficients mlw of DMAP were evaluated and plotted against the concentration of benzoyl chloride in Fig. 5. From this figure, the following correlation for m l w was obtained.
m t w = 58.7[Bz-C1] + 0.255.

Wilke and Chang and were found to be 4.80 x 10- to and 7.97 x 10- to m2/s, respectively, at 303 K. The mass transfer coefficients kL and k~. of the relevant species in the aqueous and organic phases, respectively, were predicted from the empirical correlation of Asai et al. (1983). 5. RESULTSAND DISCUSSION Figure 2 shows the plot of [DMAPI against [BDPC] [Bz-C1] with the parameter of the initial concentration [Bz-C1]o of benzoyl chloride according to eq. (8). From the slope of the straight line, the equilibrium constant k of reaction (b) in the organic solution of 1,2-dichloroethane was evaluated to be 0.86 m3/kmol at 303 K, independent of the composition of the organic phase. The distribution equilibria of DMAP and BDPC between water phase and organic phase of 1,2-dichloroethane containing benzoyl chloride were measured by varying the concentrations of DMAP and benzoyl chloride. The observed distribution equilibria are represented in Figs 3 and 4. The distribution of

(15)

From the slope of straight line in Fig. 4, the distribution coefficient m2w of BDPC was determined to be 16.4 at 303 K. This value is much larger than the value (0.255) of DMAP for 1,2-dichloroethane without benzoyl chloride-water system. Figure 6 illustrates the distribution equilibrium of DMAP for the 1,2-dichloroethane-aqueous glycine solution systems. The distribution of DMAP into the aqueous phase of DMAP increased with the concen-

10
6 i i i , i

5 i

O [Bz-CI] o = 0.085 kmol/m3 ,31 [Bz-CI]o=0.171 kmol/m3 19 [Bz-CI]o = 0.256 kmol/ma ~ [B~C~-CI]o =0 . 3 4 1

~--8
E
0

O [Bz CI] = 0.08 kmol/m3 (~ [Bz-Cl] = 0.16 kmol/m3 (B [Bz-CI] = 0.25 kmol/m3 [Bz-CI) = 0.33 kmol/m3

// / /jl

I;~

/ /

-i
O~ t/ 1 . . 2. . 3 4 ,5 [DMAP][Bz-CI] 103 (kmol2/m 6)

%
4 0 Q. 3 m~2 /

i
[~1

-6

104 (kmol/m3)

Fig. 2. Determination of equilibrium constant/( of reaction (b) at 303 K.

Fig. 4. Distribution equilibrium of BDPC for 1,2-dichloroethane containing benzoyl chloride-water system at 303 K.

25 ~ - - - ~ 4 i i i i r i i

20

EIO ~' /// / 1 /// / ~o" ,, tS~-CIJ=025.,,,o~/r.' / [] tB~a-c~j= o16,mo~/,,,3 4 5

////

o tB-~-c, = 008 kmot/m3 /

c,_o

O~ 2 4 6 [DMAP] x 103 (kmol/m 3) 8

011

012 013 014 [Bz-Cl] (kmol/m 3)

O.S

Fig. 3. Distribution equilibrium of DMAP for 1,2-dichloroethane containing benzoyl chloride-water system at 303 K.

Fig. 5. Relationship between distribution coefficient of BDPC and bulk concentration of benzoyl chloride for 1,2dichloroethane containing benzoyl chloride-water system at 303 K.

Synthesis of hippuric acid with inverse phase transfer catalyst tration of glycine. The distribution coefficients m~ of D M A P and m2 of B D P C for the actual experimental systems cannot be measured directly because B D P C reacts with glycine. Therefore, the distribution coefficients m~ of D M A P for the actual experimental systems were estimated by exchanging the intercept of eq. (15) with the distribution coefficients obtained from Fig. 6 on the basis of the assumption of the additivity. That is, rnt = 58.7 [Bz-CI-] + 2.50[Gly] + 0.255. (16)

947

O n the other hand, it was also assumed that the distribution relation of B D P C was unchanged by the glycine concentration, as well as that by benzoyl chloride concentration, and the distribution coefficients m2 of B D P C for the actual experimental systems were taken as being equal to the value of m2w. The comparisons of the overall reaction rate and yield observed for the present inverse phase transfer catalyst with those for the conventional alkaline solution method (Schotten-Baumann method) are shown in Table 1. The reaction did not substantially occur under the condition of non-catalyst, but the overall reaction rates increased with the concentration of D M A P or N a O H , the former catalytic effect being much larger than that of the latter. On the other hand,

the yield of hippuric acid based on the conversion of benzoyl chloride in the organic phase was enhanced with an increase in D M A P concentration, while it reduced with an increase in N a O H concentration owing to the hydrolysis of benzoyl chloride. Figure 7 illustrates the effect of the bulk concentration of glycine in the aqueous phase on the overall reaction rates N2 of B D P C with various initial concentration of D M A P as a parameter. The overall reaction rates, that is, the mass transfer rates N2 increase with the bulk concentration of glycine. The data points for each concentration of D M A P can be correlated by the straight line with slope equal to 0.5. When the main reaction (a) in the aqueous phase occurs in the fast pseudo first-order reaction regime, that is, y > 3, eqs (9) and (12) can be written as

N2/x/O2[Gly]b=

xfk [ B D P C ] , .

(17)

Thus, Fig. 7 confirms that this reaction system is of first order with respect to the bulk concentration of glycine in the aqueous phase. Figure 8 shows the effect of the bulk concentration of D M A P in the aqueous phase on the overall reaction rates N2 with the parameter of the initial glycine concentration. The overall reaction rates N2 may be

10

'Pf~l

i i l ~

[ ] [Gly] = 0,5 k m o l / m

s c,l

~E'31%2

~/

" tG,y] = o.3 kmo,/r.~

V [Gly} = 0.1 k m o l / m 3 -

E
0

E %
X

ID

[ DMA P ] o = 0 . 0 5 k m o l / m 3 [DMAP] o = 0.03 kmol/m 3 [ DMA P ] o = 0.01 k m o l / m 3 ~ J i i IILIJ

0.1
"0 1 2 3 4 [DMAP] 10 2 (kmol/m 3)

J iPiiI

0.1

[Gly]b (kmol/m 3)

Fig. 6. Distribution equilibrium of DMAP for 1,2-dichloroethane-aqueous glycine solution system.

Fig. 7. Effect of bulk concentration of glycine in aqueous phase on overall reaction rates at 303 K and I-Bz-C1]o = 0.256 kmol/m 3.

Table 1. Effect of NaOH and DMAP catalysts on overall reaction rates and yield Catalyst 0.05 kmol/m s DMAP 0.01 kmol/m s DMAP 3.0 kmol/m 3 NaOH 1.0 kmol/m s NaOH 0.2 kmol/m s NaOH Non-catalyst Overall reaction rate (kmol/m 2 s) 9.27 x 10 -s 3.85 10 -8 9.12 10 -8 5.33 10 -8 1.97 10 -8 1.42 10-11 Yield (%) 94 92 49 58 63 _

Note: temperature, 303 K; organic phase, [Bz-Cl]o = 0.085 kmol/m3; aqueous phase, [Gly]o = 0.1 kmol/m 3.

948
7 i i i i i i

S. ASAI et al.
i i

[] r~ [] ~

[Gly] o = [GlY]o = [Gly]o = [GlY]o =

0.8 0.5 0.3 0.1

kmol/m 3 kmol/m a kmol/m a kmol/m3

? ~ j

~q E

-5

%
Z
z
I

/ //~' W/ y
I I I I

o~ data~nFig. 7 [] [] II] [] data in Fig. 8 ~ , data in Fig. 9

~ I I I L

o.o4

0.ha

0.~2

[DMAPlb (kmol/ma) Fig. 8. Effect of bulk concentration of DMAP in aqueous phase on overall reaction rates at 303 K and [Bz-C1]o = 0.256 kmol/m3.

[ B D P C ] i > 102 ( k m o l . m -3)

Fig. 10. Determination of second-order reaction rate constant k from all experimental data at 303 K.

~4 -53 ~'2

A [DMAPlo = 0.05 kmol/m 3 A [DMAPlo = 0.03 kmol/m 3 J" [DMAP]o = 0.01 kmoq/m 3

Fig. 10. All experimental values are proportional to the aqueous phase interfacial concentration [BDPC]i, indicating that the reaction is first order with respect to BDPC. From the slope of the straight line, the second-order reaction rate constant k was determined to be 6.50 m3/(kmol s) at 303 K.
6. CONCLUSION

7
Z

0~1 0~2 0t3 0~4 [Bz-CI]b (kmol/m3)

0.5

Fig. 9. Effect of bulk concentration of benzoyl chloride in organic phase on overall reaction rates at 303 K and [Gly]0 = 0.3 kmol/m3.

seen to increase with the bulk concentration of DMAP, as expected. Figure 9 represents the overall reaction rates N2, which are plotted against the bulk concentration of benzoyl chloride in the organic phase for the three initial concentrations of DMAP. The overall reaction rates N2 for each DMAP concentration may be seen to increase with the bulk concentration of benzoyl chloride, but the degree of their increase decreases with an increase in the bulk concentration of benzoyl chloride. This result may be explained by the competing effect that benzoyl chloride not only acts as a reactant to form BDPC in the organic phase, but also brings about the unfavorable distribution of DMAP into the organic phase, as shown in Figs 3 and 5. The left-hand side of eq. (17) should be proportional to the interfacial concentration [BDPC]~ of BDPC in the aqueous phase. Then, the reaction rate constant k can be determined from the slope of the straight line of the N 2 / ~ vs [BDPC]~ plots. The plot of eq. (17) based on the data for all runs is shown in

The synthesis of hippuric acid from benzoyl chloride and glycine by using inverse phase transfer catalysis of 4-dimethylaminopyridine (DMAP) was investigated in a heterogeneous liquid-liquid system. This reaction could be accelerated remarkably by the addition of DMAP, instead of alkali as used in the conventional Schotten-Baumann method. The yield of product, hippuric acid, was also improved by adding DMAP. The observed overall reaction rates between glycine and the salt, 1-benzoyl-4-dimethylaminopyridinium chloride (BDPC), which is formed by the reaction of benzoyl chloride with DMAP in the organic phase, were proportional to the aqueous phase interfacial concentration of BDPC. Its interracial concentration was a unique function of the concentrations of DMAP and glycine in the aqueous phase and of benzoyl chloride in the organic phase. The observed overall reaction rates were reasonably explained by the proposed analytical solution for the irreversible fast pseudo first-order reaction allowing for the mass transfer resistance of the relevant reaction species. The reaction rate constant was evaluated to be 6.50 ma/(kmol s) at 303 K, independent of the concentrations of DMAP and glycine in the aqueous phase and of benzoyl chloride in the organic phase.

Acknowledgement--The authors would like to thank Koei Chemical Co., Ltd., Japan for providing 4-dimethylaminopyridine.
D K
NOTATION diffusivity, m 2 / s

equilibrium constant, m3/kmol

Synthesis of hippuric acid with inverse phase transfer catalyst k k' kL kl k_~ m N z [ ]
Greek letters

949

second-order reaction rate constant, m3/(kmol s) pseudo first-order reaction rate constant defined by eq. (2), s-1 mass transfer coefficient, m / s forward reaction rate constant, sreverse reaction rate constant, m 3/ (kmol s) distribution coefficient between organic and aqueous phases, dimensionless mass transfer rate, kmol/(m 2 s) distance from interface, m concentration, k m o l / m 3

2 3

BDPC benzoyl chloride

REFERENCES

dimensionless number defined by eq. (12) film thickness, m

Superscript -organic phase Subscripts b i j w 0 1

bulk interface species j water initial DMAP

Asai, S., Hatanaka, J. and Uekawa, Y., 1983, Liquid-liquid mass transfer in an agitated vessel with a flat interface. J. Chem. Enono Japan 16, 463-469. Asai, S., Nakamura, H. and Furuichi, Y., 1992, Alkaline hydrolysis of n-butyl acetate with phase transfer catalyst Aliquat 336. A.I.Ch.E.J. 38, 397-404. Dehmlow, E. V. and Dehmlow, S. S., 1983, Phase Transfer Catalysis. Verlag Chemie, Weinheim. Fife, W. K., Zeldin, M. and Tian, C.-X., 1987, Pyridinyl- and 1-oxypridinyl-substituted silanes and siloxanes: new catalysts for interracial transacylation reactions. Adv. Chem. Ser. 224, 99-111. Keller, W. E., 1986, Phase Transfer Reactions. Georg Thieme, Stuttgart. Mathias, L. J. and Vaidya, R. A., 1986, Inverse phase transfer catalysis. First report of a new class of interracial reactions. J. Am. Chem. Soc. 108, 1093-1094. Rubinsztajn, S., Zeldin M. and Fife, W. K., 1990, New transacylation catalysts: silanes and siloxanes functionalized with 4-(dialkylamino)pyridine moieties. Macromolecules 23, 4026-4027. Starks, C. M. and Liotta, C., 1978, Phase Transfer Catalysis. Academic Press, New York. Wilke, C. R. and Chang, P., 1955, Correlation of diffusion coetticient in dilute solution. A.I.Ch.E.d. 1, 264-270. Zeldin, M., Fife, W. K., Rubinsztajn, S. and Tian C.-X., 1989, Siloxane polymers and copolymers with pendant 1-oxypyridin-3-yl groups as transacylation catalyst. Polym. Mater. Sci. Enon9 61, 99-100.