Paper: 90008098
Symposium: 60: Phase-Transfer Catalysis
Hotel: Hilton Hawaiian Village, Mid-Pacific - Coral
Room: Ballroom IV
Day: Thursday AM
Time: 8:05
Invited: Y
Oral
Introduction: M. Halpern
Asymmetric phase transfer catalysis utilizing the quaternary ammonium salts derived
from cinchona alkaloids. Professor Takayuki Shioiri, Dr. Shigeru Arai. Faculty of
Pharmaceutical Sciences, Nagoya City University, Tanabe-Dori, Mizuho-Ku, Nagoya 467-8603,
Japan, 81-52-834-4172, shioiri@phar.nagoya.cu.ac.jp. The quaternary ammonium salts derived
from cinchona alkaloids now occupy the central position in asymmetric phase transfer catalysis.
Utilizing these salts as catalysts, we have developed the following asymmetric phase transfer
reactions: asymmetric alkylation of a-fluorotetralone, asymmetric aldol reaction of enol silyl
ethers, asymmetric cyclopropanation, asymmetric Darzens reaction, asymmetric epoxidation,
asymmetric a-hydroxylation of cyclic ketones, and asymmetric isomerization of alkynes to allenes.
Recent results in this area will be presented.
1

Paper: 90004877
Symposium: 60: Phase-Transfer Catalysis
Hotel: Hilton Hawaiian Village, Mid-Pacific - Coral
Room: Ballroom IV
Day: Thursday AM
Time: 8:35
Invited: Y
Oral
Introduction: M. Halpern
New Results in Applications and Mechanism of Phase-Transfer Catalysis. Professor
Mieczyslaw Makosza. Polish Academy of Sciences, Institute of Organic Chemistry, Kasprzaka
44/52, Warsaw, Warsaw, Poland, +48 22 632 6681, icho-s@icho.edu.pl. Phase-Transfer Catalysis
(PTC) is a well established and general methodology in organic synthesis, particularly for reactions
of anionis species. There are however some important reactions in this category such as base
induced ?-elimination and synthesis of organic fluorocompounds via replacement of leaving groups
with fluoride anions for which application of PTC is limited and inefficient. Cocatalytic systems for
these reactions, which offer significant advantages were developed and will be presented and
discussed along with some new reactions of carbanions. New synthesis of substituted
tetrahydrofurans via PTC reactions of 4-halobutyronitriles and mechanism of generation of the
intermediate carbanions will be presented.
2

Paper: 90006944
Symposium: 60: Phase-Transfer Catalysis
Hotel: Hilton Hawaiian Village, Mid-Pacific - Coral
Room: Ballroom IV
Day: Thursday AM
Time: 9:05
Invited: Y
Oral
Introduction: M. Halpern
Phase-Transfer Catalysis in Supercritical Fluids. Dr. Charles L. Liotta, Dr. Charles A. Eckert,
Mr. Kris Griffith, Ms. Angie Dillow, Mr. David Suleiman, Ms. Karen Chandler, Ms. Christy Culp, Mr.
Josh Brown, Ms. Heather Lesutis, Mr. David Bush, Mr. Barry West, Mr. David Lamb. Georgia
Institute of Technology, School of Chemistry & Chemical Engineering, Atlanta, Ga, USA, 404-894-7035,
charles.liotta@carnegie.gatech.edu. Phase-transfer catalysis (PTC) is a powerful and widely
used technique for conducting heterogeneous reactions between two or more reactants in two or
more immiscible phases. Examples of reactions conducted under solid-liquid and liquid-liquid PTC
conditions are well documented in the literatures. This presentation explores examples of PTC
reactions using supercritical fluids. PTC substitution and alkylation reactions between solid and
supercritical fluid phases will be discussed.
3

Paper: 99000138
Symposium: 60: Phase-Transfer Catalysis
Hotel: Hilton Hawaiian Village, Mid-Pacific - Coral
Room: Ballroom IV
Day: Thursday AM
Time: 9:35
Invited: Y
Oral
Introduction: M. Halpern
Activation of Aromatic C-Cl and C-H Bonds by Pd Catalysts in the Presence of Phase
Transfer Agents. Professor Yoel Sasson, Dr. Sudip Mukhopadhyay, Dr. Gadi Rothenberg, Mrs.
Diana Gitis. The Hebrew University of Jerusalem, Casali Institute of Applied Chemistry, Jerusalem,
Israel, 972-25667065, ysasson@vms.huji.ac.il. Phase transfer agents demonstrate a remarkable
effect on the efficacy of palladium catalysts in C-C bond formation reactions. We have studied the
effect of PTCs (quaternary salts and PEGs) on the rate and selectivity of: [1] Reductive
homocoupling of chlorobenzenes to biphenyls in presence of Pd/C catalyst using various
reductants. [2] Reductive cross-coupling of chlorobenzenes with electron poor aromatics or
heteroaromatics catalyzed by Pd/C with zinc. [3] Oxidative coupling of benzenes in presence of
PdCl2 using air or chlorobenzenes as primary oxidant. The role of PTC in these systems is
attributed to: [1] Rapid removal of HCl from the Pd surface thus assisting in the reduction process
Pd(II) -> Pd(0). [2] Stabilizing of Pd(0) nanoparticles in solution thus avoiding catalyst
deactivation through aggregation. [3] Formation of a "membrane" covering the Pd surface which
allows the flow of electrons but retard the transport of hydrogen. The latter is the main cause for
side hydrodehalogenation reactions.
4

Paper: 90010253
Symposium: 60: Phase-Transfer Catalysis
Hotel: Hilton Hawaiian Village, Mid-Pacific - Coral
Room: Ballroom IV
Day: Thursday AM
Time: 10:05
Invited: Y
Oral
Introduction: M. Halpern
Synthesis of polymers containing pendant reactive chloromethyl groups by the
polyaddition of bisepoxides with diacyl chlorides and their chemical modification using
PTC. Professor Tadatomi Nishikubo, Other Atsushi Kameyama, Other Urara Inagaki. Kanagawa
University, Faculty of Engineering, 3-27-1 Rokkakubashi, Kanagawa-ku, Yokohama, Kanagawa,
Japan, 81-45-491-7915, nisikubo@cityfujisawa.ne.jp. The polyesters with pendant reactive
chloromethyl groups were synthesized by the polyaddition of bisepoxides with diacyl chlorides
catalyzed by quaternary onium salts as polymerization catalysts under mild conditions. The
catalytic activity of the used quaternary onium salts was investigated in details. The chemical
modification of the reactive polyesters (P-1) with certain nucleophilic reagents such as sodium
azide or potassium phthalimide using PTC was also examined. In addition, photo-functional
polymers with pendant cinnamoyl group or norboronadine group were successfully synthesized by
the polymer reaction of P-1 with potassium cinnamate or potassium 3-phenyl-2,5-norbornadiene-2-
carboxylate, which has a solar energy storage function. The behavior of the polymer reaction of
P-1 with KNBD using TBAB in toluene was investigated in details.
5

Paper: 90005755
Symposium: 60: Phase-Transfer Catalysis
Hotel: Hilton Hawaiian Village, Mid-Pacific - Coral
Room: Ballroom IV
Day: Thursday AM
Time: 10:35
Invited: Y
Oral
Introduction: M. Halpern
PTC in the Plastics Industry. Dr. Daniel Brunelle, Dr. Eugene Boden, Mr. Peter Phelps. GE
Corporate Research and Development, Performance Polymers Program, 1 Research Circle,
Sehenectady, NY, USA, 518-387-5592, brunelle@crd.ge.com. Phase transfer catalysis (PTC) has
found numerous uses in industry, and has streamlined and simplified many processes in the
manufacture of plastics. The mechanism of the interfacial preparation of polycarbonate, can be
completely changed by substitution of the traditional tertiary amine catalysts for a true PTC; the
PTC affords essentially no hydrolysis reactions. Bifunctional catalysts have recently been disclosed
featuring positive features of both types of catalyst. Thermally stable hexaalkylguanidinium salts,
are being used in the manufacture of silicones and polyetherimides, and have improved yields and
conversions, while limiting by-product formation. These and other results will be discussed in this
paper.
6

Paper: 90005922
Symposium: 60: Phase-Transfer Catalysis
Hotel: Hilton Hawaiian Village, Mid-Pacific - Coral
Room: Ballroom IV
Day: Thursday AM
Time: 11:05
Invited: N
Oral
Introduction: M. Halpern
Phase Transfer Catalysed (PTC) Reactions of Some C-H Acids with Di- and
Trichloroethylene. Professor Andrzej Jonczyk. Warsaw University of Technology, Faculty of
Chemistry, Koszykowa 75, Warsaw, Warsaw, Poland, +48 22 628 2741, anjon@ch.pw.edu.pl. We
have found that benzyl ketones, substituted at benzyl carbon, and 2-phenylalkanals react with
trichloroethylene (TRI) in the presence of conc. aq. alkali metal hydroxide or powdered potassium
carbonate and a PT catalyst, to afford C- or O-dichlorovinylated products, respectively. Other C-H
acids, namely 1,3-dialkylindenes, isoquinoline Reissert compound and some esters are also prone
to react with TRI with formation of the same type of products. The process is restricted to methine
C-H acids and consists in trans-addition (major pathway) of carbanions to in situ generated
dichloroacetylene with following protonation of highly basic vinyl anions thus formed. On the other
hand, E-dichloroethylene enters reaction with carbanions generated from 2-arylalkanenitriles and
1,3-dialkylindenes to give E-2-chlorovinylated products. This reaction takes place according to
addition-elimination pathway. Thus, PTC is a simple and efficient method for 2-chloro- and 1,2 -dichlorovinylation
of methine C-H acids.
7

Paper: 99000212
Symposium: 60: Phase-Transfer Catalysis
Hotel: Hilton Hawaiian Village, Mid-Pacific - Coral
Room: Ballroom IV
Day: Thursday PM
Time: 1:05
Invited: Y
Oral
Introduction: C. Starks
Phase transfer catalysis applications to organic industrial synthesis. Mr. D. Landini, Mr.
D. Albanese, Mr. V. Lupi, Mr. A. Maia, Mr. M. Penso. University-Via Venezian, Organic and
Industrial Chemistry , Milan, Italy, +39-02-2364369, Dario.Landini@unimi.it. A survey of relevant
applications of liquid-liquid and solid-liquid phase transfer catalysis ( LL-and SL-PTC ),recently
realized in our laboratory to organic industrial synthesis,will be presented and discussed.In
particular,the generation "in situ" of alkyl and aryl sulphonamidides,and reactions of these
azaanions with epoxides and glycidyl esters will be described.LL- or SL-PTC protocols for the
synthesis of N-activated aziridines,3,4-dihydro-2H-1,4-benzossazines, 2,6-disubstituted
morpholines and quinoxalines,and for the selective N-monoalkylations of alfa-amino esters will be
reported.
8

Paper: 90009405
Symposium: 60: Phase-Transfer Catalysis
Hotel: Hilton Hawaiian Village, Mid-Pacific - Coral
Room: Ballroom IV
Day: Thursday PM
Time: 1:35
Invited: Y
Oral
Introduction: C. Starks
Unnatural Amino Acid and Peptide Synthesis by PTC. Professor Martin J. O'Donnell, Dr.
William L. Scott. Indiana University-Purdue University at Indianapolis, Department of Chemistry,
402 N. Blackford St., Indianapolis, IN, USA, 317-274-4701, odonnell@chem.iupui.edu. The use of
phase-transfer catalysis (PTC) in the alkylation and Michael addition of Schiff base esters of
glycine provides convenient large- or small-scale routes to a variety of amino acid derivatives. The
various levels of selectivity realized in these reactions will be discussed as will the development of
catalytic enantioselective variants. The methodology has also been extended to the resin-bound
synthesis of unnatural amino acids and peptides by side-chain introduction during a normal solid-phase
peptide synthesis (SPPS).
9

Paper: 90001935
Symposium: 60: Phase-Transfer Catalysis
Hotel: Hilton Hawaiian Village, Mid-Pacific - Coral
Room: Ballroom IV
Day: Thursday PM
Time: 2:05
Invited: Y
Oral
Introduction: C. Starks
EPOXIDATION OF 5-VINYL-2-NORBORNENE UNDER PHASE-TRANSFER CATALYSIS
CONDITIONS. Dr. Maw-Ling Wang, Mr. Tsuan-Hsuan Huang. National Chung Cheng Univ,
National Chung Cheng University, 160 San-Hsien Village, Ming-Hsiung, Chiayi, Taiwan, Taiwan,
886-5-272-0404, chmmlw@ccunix.ccu.edu.tw. Epoxidation of 5-vinyl-2-norbornene was carried
out in an organic solvent/water two-phase medium under phase-transfer catalysis conditions.
Quaternary ammonium salts were employed as the phase-transfer catalysts, and sodium tungstate
and phosphoric acid were served as the cocatalyst for epoxidation. Further, low cost hydrogen
peroxide was found to be an active oxidant in which the pollution problem was minimized. A
complex of the phase-transfer catalyst, cocatalyst and hydrogen peroxide was first prepared in a
lquid solution. Effect of the reaction conditions, such as agitation speed, quaternary ammonium
salts, polarity of the organic solvents, pH-value and temperature on the conversion of 5-vinyl-2-norbornene
and selectivity were investigated in detail. Only epoxidation of the single double bond
of 5-vinyl-2-norbornene was detected. The reaction can be described by a pseudo-first order rate
law. A 90% conversion of 5-vinyl-2-norbornene was obtained under appropriate conditions.
10

Paper: 90007538
Symposium: 60: Phase-Transfer Catalysis
Hotel: Hilton Hawaiian Village, Mid-Pacific - Coral
Room: Ballroom IV
Day: Thursday PM
Time: 2:35
Invited: Y
Oral
Introduction: C. Starks
Production of Benzaldehyde: A Case Study in A Possible Industrial Application of Phase
Transfer Catalysis. Professor L.K. Doraiswamy, Mr. Justinus Satrio. Iowa State University,
Chemical Engineering, Sweeney Hall, Ames, Iowa, USA, 515-294-2689, dorai@iastate.edu. The
conventional method of producing benzaldehyde by direct oxidation of toluene has a major
drawback: low conversion to achieve high selectivity. Phase transfer catalysis (PTC) may be used
as an alternative route for benzaldehyde production. In the present study, three routes to produce
benzaldehyde from benzyl chloride in the liquid phase by using PTC have been studied. Kinetic
data were obtained and reaction modeling has been attempted. Based on the results of this study
and the available information on the conventional route, process simulations have been carried out
for all the processes. While PTC-based processes offer advantages, the study shows that the
conventional route appears to be the marginally preferred one with current conversions,
selectivities, and catalyst costs. However, even minor improvements in one or two PTC steps can
tilt the choice in favor of a PTC route.
11

Paper: 90005841
Symposium: 60: Phase-Transfer Catalysis
Hotel: Hilton Hawaiian Village, Mid-Pacific - Coral
Room: Ballroom IV
Day: Thursday PM
Time: 3:05
Invited: Y
Oral
Introduction: C. Starks
Recent advances on polymeric phase transfer catalysts. Professor Masao Tomoi.
Yokohama National University, Dept. of Chemistry and Biotechnology, 79-5 Tokiwadai, Hodogaya-ku,
Yokohama, Kanagawa, Japan, 81-45-339-3960, mtomoi@ynu.ac.jp. Phase transfer catalysts
fixed to insoluble polymers are useful as well as soluble phase transfer catalysts for organic
reactions. However, the activity of the polymer-supported phase transfer catalysts is lower than
the corresponding soluble catalysts. In case of the reaction using the polymer-supported catalyst,
the reaction system consists of substrate phase (liquid), reagent phase (liquid or solid), and
catalyst phase (solid). The catalytic activity, therefore, is mainly dependent on both the diffusion
of substrate and reagent in the catalyst particle and the inherent reactivity of active site. Here, a
means of improving the activity of polymer-supported phase transfer catalysts, especially the
effect of introduction of spacer chains between the backbone of the carrier polymer and the active
site, is discussed.
12

Paper: 66741310
Symposium: 60: Phase-Transfer Catalysis
Hotel: Hilton Hawaiian Village, Mid-Pacific - Coral
Room: Ballroom IV
Day: Thursday PM
Time: 3:35
Invited: N
Oral
Introduction: C. Starks
The role of the solid surface and its influence on kinetics in solid-liquid phase-transfer
catalysis. The study of nucleophilic substitution with solid halides. Professor Sergei Yufit
S, Mr. Sergei Zinovyev S. Leninsky pr. 47, Moscow, Russia, Russia, +07 (095) 1355328,
yufit@ioc.ac.ru, ane@glasnet.ru. The mechanism and topology of the solid-liquid (s/l) phase-transfer
catalysis (PTC) are still one of the most important and controversial issues in PTC. S/l
systems usually involve mass-transfer and surface poisoning or modification effects, all of which
make the kinetic behavior of the s/l PTC closely resemble the heterogeneous processes.The kinetic
behavior of the s/l PTC nucleophilic substitution reactions of aliphatic halides, and of sulfonates
with solid salts were investigated, and some important mechanistic conclusions were drawn. It was
shown that such reactions are likely to proceed through the formation of the intermediate binary
and ternary complexes, adsorbed on the solid surface.The complexity of the corresponding PTC
catalytic schemes makes it possible for some principles of enzyme kinetics to be successively
applied. The kinetic data analyses along with the discrimination of other kinetic models allowed us
to develop a model of 'initial burst' which could be applied to s/l PTC to estimate the mass-transfer
and surface poisoning. A detailed kinetic study on the influence of various reaction conditions on
the s/l system was also performed, as was a spectrometric study on the structure and composition
of the reacting surface.
13

Paper: 90004973
Symposium: 60: Phase-Transfer Catalysis
Hotel: Hilton Hawaiian Village, Mid-Pacific - Coral
Room: Ballroom IV
Day: Thursday PM
Time: 4:05
Invited: N
Oral
Introduction: C. Starks
Alkane Activation under Phase-Transfer Catalysis. Professor Peter R. Schreiner, Mr. Oliver
Lauenstein, Professor Andrey A. Fokin. University of Georgia, Chemistry, 1001 Cedar St., Athens,
GA, USA, (706) 542-9454, prs@chem.uga.edu. Recently, we reported a phase-transfer catalyzed
method to transform even the simplest alkanes into their corresponding bromides.(1) We
meanwhile also developed the first efficient iodination of alkanes.(2) As these reactions offer new
avenues for solving the long-standing problem of C-H-activation of paraffins, the scope and
limitation as well as the mechanistic implications of these approaches are presented. These
methods are valuable for the production of otherwise not as easily accessible alkyl iodides which
useful in the pharmaceutical industry. (1) Schreiner, P. R., Lauenstein, O., Kolomitsyn, I. V.; Nadi,
S.; Fokin, A. A. Angew. Chem. Int. Ed. Engl. 1998, 37, 1895-1897 see also Chem. Eng. News
1998, July 13, p. 55. (2) Schreiner, P. R.; Lauenstein, O.; Butova, E. D.; Fokin, A. A Angew.
Chem. Int. Ed. Engl. 1999, 38, 2786-2788 see also Chem. Eng. News 1999, December 6, p. 44.
14

Paper: 64462720
Symposium: 60: Phase-Transfer Catalysis
Hotel: Hilton Hawaiian Village, Mid-Pacific - Coral
Room: Ballroom IV
Day: Friday AM
Time: 8:05
Invited: Y
Oral
Introduction: Shioiri
Mechanisms of s/l and l/l PTC in base-containing systems. Professor Felix Sirovski. 47
Leninsky pr., Moscow, Moscow Region, Russia, 7-095-1355328, sirovski@gol.ru. The mechanisms
of dichlorocarbene addition in s/l and l/l systems are discussed.For the s/l system the influence of
the formation of the crust of the inorganic product on the surface of the reagent particle and the
effect of water content are discussed. In the l/l system we tried to distinguish betwen the
interfacial and extraction mechanisms using the Levenspiel's model of two-phase reaction.
According to it, if the reaction proceeds directly at the inteface then it should be first-order, and if
it proceeds in the boundary film - second order. The reaction proceeded according to the second-order
rate law. So it seems that the reaction did proceed in the film after all. The data obtained on
solvent effect in this and other reactions are also discussed.
15

Paper: 78004250
Symposium: 60: Phase-Transfer Catalysis
Hotel: Hilton Hawaiian Village, Mid-Pacific - Coral
Room: Ballroom IV
Day: Friday AM
Time: 8:35
Invited: Y
Oral
Introduction: Shioiri
Achieving Effective Separation of Phase Transfer Catalysts from Products and Minimizing
Aqueous Waste. Dr. Reuben Grinstein, Dr. Marc Halpern. 2430 N. Huachuca Drive, Tucson,
Arizona, USA, +1 520 624 0912, reuben.grinstein@cognis-us.com. New data have been generated
which describe the distribution of three commercial quaternary ammonium (quat) phase-transfer
catalysts between five organic "solvents" and two aqueous phases. Examination of these data
strongly suggest that effective catalyst separation from the product can be achieved in a variety of
cases in which it is desirable to extract the catalyst into water OR have the catalyst remain in the
organic phase. It is shown that extraction of the catalyst into water (the most common method of
separating catalyst in commercial and laboratory applications) can be improved by up to three
orders of magnitude while using only half of the water washes. In many cases, residual levels of <
1 ppm of water soluble catalysts can be achieved with one or two water washes. In some cases,
replacement of an existing catalyst system may be worthwhile to achieve desirable catalyst
separation.
16

Paper: 90010426
Symposium: 60: Phase-Transfer Catalysis
Hotel: Hilton Hawaiian Village, Mid-Pacific - Coral
Room: Ballroom IV
Day: Friday AM
Time: 9:05
Invited: Y
Oral
Introduction: Shioiri
Hydrogen peroxide oxidation of various organic compounds catalyzed by
heteropolyoxometalates having phase-transfer function. Professor Yasutaka Ishii. Kansai
University, Dept. of Applied Chemistry, Kansai University, Suita, Osaka, Japan, +81-6-6339-4026,
ishii@ipcku.kansai-u.ac.jp. Hydrogen peroxide oxidations of various unsaturated compounds such
as alkynes, allenes, and enol ethers, which are difficult to carry out by conventional methods, were
examined using heteropolyoxometalates substituted by quarternary ammonium cation. For
instance, alkynes with aqueous hydrogen peroxide in the presence of a catalytic amount of
cetylpyridinium peroxotungstophosphate (PCWP) were converted to ?,?-unsaturated ketones in
good yields. Allenes in the presence of alcohols were oxidized to the corresponding ?-alkoxy
ketones. Dehomologation of aldehydes has been first successfully achieved via oxidative cleavage
of silyl enol ethers, derived from aldehydes and trimethylchlorosilane. (Me 3 SiCl), using aqueous
hydrogen peroxide under the influence of PCWP under phase-transfer conditions. Treatment of 1-[(
trimethylsilyl)oxy]-1-octene, derived from octanal and Me 3 SiCl, with 35% H 2 O 2 catalyzed by
PCWP at room temperture afforded the one-carbon shorter aldehyde, heptanal, in 79% yield.
17

Paper: 68692330
Symposium: 60: Phase-Transfer Catalysis
Hotel: Hilton Hawaiian Village, Mid-Pacific - Coral
Room: Ballroom IV
Day: Friday AM
Time: 9:35
Invited: N
Oral
Introduction: Shioiri
Selectivity and Kinetics of the Catalytic Multiphase Hydrodehalogenation of Halo-Aromatics.
Professor Pietro Tundo, Dr. Alvise Perosa, Mr. Sergei Zinovyev. Dorsoduro 2137,
Venezia, VE, Italy, +39-041-257 8620, tundop@unive.it. A novel multiphase catalytic system
allows the rapid, efficient, and quantitative replacement of halogens (e.g. chlorine) from halo-aromatics,
in the presence of a phase-transfer (PT) agent, and under mild conditions (1 atm H2
and 50 ?C). This novel reaction system was investigated from (a) the synthetic, and (b) the
mechanistic point of view.(a) The reaction allows to control the selectivity of chlorine removal
against the competitive reduction of the aromatic ring, or of other reduction-sensitive groups (e.g.
carbonyl) present in the reagent. This is achieved by varying simple reaction parameters, such as
for example, the nature of the supported-metal catalyst (Pd or Pt), the nature and amount of the
PT agent, the composition and acidity of the aqueous phase.(b) The kinetic behavior and selectivity
was studied in terms of the rate constants, and the mechanistic conclusions suggest that the PT
agent forms a third liquid phase over the surface of the metal supported catalyst, thereby
modifying the reaction surface by changing the geometry of the substrate adsorption on the solid
metal-catalyst surface.
18

Paper: 90010264
Symposium: 60: Phase-Transfer Catalysis
Hotel: Hilton Hawaiian Village, Mid-Pacific - Coral
Room: Ballroom IV
Day: Friday AM
Time: 10:05
Invited: Y
Oral
Introduction: Shioiri
Design of a C 2 -symmetric chiral phase transfer catalyst for practical a a-amino acid
synthesis. Professor Keiji Maruoka. Kyoto University, Chemistry, Department of Chemistry,
Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto, Japan, +81-75-753-4041,
maruoka@kuchem.kyoto-u.ac.jp. Since the pioneering work of O'Donnell et al. in 1989,
asymmetric synthesis of ?-amino acids by enantioselective alkylation of a prochiral protected
glycine derivative using a chiral phase transfer catalyst has provided an attractive method of both
natural and unnatural amino acids. However, almost all the elaborated chiral phase transfer
catalysts reported so far have been restricted to cinchona alkaloid derivatives, which unfortunately
constitutes a major difficulty in rationally designing and fine-tuning of catalysts to attain sufficient
reactivity and selectivity for various chemical transformations under phase transfer catalyzed
conditions. Accordingly, sructurally rigid, chiral spiro ammonium salts derived from commercially
available (S)-binaphthol have been designed as a new C 2 -symmetric chiral phase transfer catalyst
and successfully applied to the highly efficient, catalytic enantioselective alkylation of tert-butyl
glycinate-benzophenone Schiff base under mild phase transfer conditions. Various alkyl halides
(RX) were employable where enantioselectivities generally exceeded 90% ee, indicating the
remarkable potential and generality of the present system.
19

Paper: 90007315
Symposium: 60: Phase-Transfer Catalysis
Hotel: Hilton Hawaiian Village, Mid-Pacific - Coral
Room: Ballroom IV
Day: Friday AM
Time: 10:35
Invited: Y
Oral
Introduction: Shioiri
Chain-Growth Polycondensation in Solid-Liquid Phase with Phase Transfer Catalysts.
Professor Tsutomu Yokozawa. Kanagawa University, Applied Chemistry, Rokkakubashi,
Kanagawa-ku, Yokohama, Japan, +81-45-413-9770, yokozawa@cc.kanagawa-u.ac.jp. We have
been studying chain-growth polycondensation that proceeds in a chain polymerization manner
from an initiator yielding well-defined condensation polymers. In this paper, we report the
polymerization of 4-bromomethyl-2-octoxybenzoic acid potassium salt (1) dispersed in organic
solvent with a phase transfer catalyst in the presence of 4-nitrobenzyl bromide (2) as an initiator.
In the polymerization of 1 with 18-crown-6 ether and 2 in acetone, polymers with a controlled
molecular weight and a narrow molecular weight distribution were obtained. The ratios of the
initiator residue to the terminal group in polymers were almost 1:1 during polymerization, and the
molecular weight increased in proportion to the monomer conversion, indicating that the
polycondensation of 1 proceeded from the initiator in a chain polymerization manner. The use of
tetrabutylammonium iodide instead of crown ether also resulted in similar polymerization behavior.
20

Paper: 90004868
Symposium: 60: Phase-Transfer Catalysis
Hotel: Hilton Hawaiian Village, Mid-Pacific - Coral
Room: Ballroom IV
Day: Friday AM
Time: 11:05
Invited: N
Oral
Introduction: Shioiri
Phase Transfer Alkylation of 2-Arylalkanenitriles revisited. Dr. Michal Fedorynski. Warsaw
University of Technology, Chemistry, Koszykowa 75, Warsaw, Warsaw, Poland, +48 22 621 3720,
elfed@chemix.ch.pw.edu.pl. Phase transfer catalysis is the best practical procedure for alkylation of
carbanions of arylacetonitriles (1) and their derivatives. High yields of monoalkylated products are
obtained with the use of primary alkyl bromides as alkylating agents, 50% aq NaOH as base and
benzyltriethylammonium chloride (TEBA) as catalyst. However: (a) with sec-alkyl bromides, the
yields are usually low (<60%); (b) the introduction of a second alkyl group to the 2-arylalkanenitriles
(2) sometimes proceeds with difficulty; (c) with 1,3-dibromopropane, yields of 1-aryl-
1-cyanocyclobutanes are low; (d) the use of 1,2-dichloro- or dibromoethane for the
cyclopropanation of (1) or for 2-haloethylation of (2) is often impossible - dehydrohalogenation of
dihaloalkane proceeds instead. We discovered that a simple change of 50% NaOH for 60% KOH,
and of the classical catalyst TEBA for tetrabutylammonium bromide overcomes all the difficulties
mentioned above. Isopropylation, sec-butylation, dialkylation and cycloalkylation of (1) with 1,3-dibromopropane
and 1-bromo-2-chloroethane proceeds with high yields. Alkylation of (2) with 1-bromo-
2-chloroethane or 1-bromo-3-chloropropane allows for the preparation of 2-aryl-2-alkyl-?-chloroalkanenitriles
with good yields. Most of these products are important intermediates in the
pharmaceutical industry.
21

Paper: 90009350
Symposium: 60: Phase-Transfer Catalysis
Hotel: Hilton Hawaiian Village - Tapa
Room: Iolani VII
Day: Saturday PM
Time: 1:00
Invited: N
Poster
Introduction:
Phase Transfer Catalysis for Tandem Synthesis of Bifunctional Molecules for Nonlinear
Optical Applications. Professor Xiu Ren Bu, Mr. Xing Li, Mr. Javier Santos, Dr. Eric A. Mintz,
Mr. Richard Mason. Clark Atlanta University, Chemistry, James P. Brawley , Atlanta, GA, USA, 404
880 6890, xbu@cau.edu. Phase transfer catalysis has been found to be effective in momo-N-alkylation
of conjugated primiary amines, in particular Disperse Orange 3 by motif-bearing
halides. A series of bifunctional molecules has been synthesized through the methodology using
PTC conditions. These molecules are potential photorefractive because they possess both
nonlinear optical chromophores and charge transporting components.
22

Paper: 90010231
Symposium: 60: Phase-Transfer Catalysis
Hotel: Hilton Hawaiian Village - Tapa
Room: Iolani VII
Day: Saturday PM
Time: 1:00
Invited: N
Poster
Introduction:
Efficient In Situ generation of quaternary ammonium fluorides under phase-transfer
conditions: application to catalytic asymmetric aldol reactions. Professor Kanae Doda,
Professor Takashi Ooi, Professor Keiji Maruoka. Hokkaido Univ., Chemistry, Dept. of Chem.,
Graduate School of Sci., Kyoto Univ., Sakyo-ku, Kyoto, Kyoto, Japan, 81-(0)75-753-4000,
kanaed@kuchem.kyoto-u.ac.jp. Quaternary ammonium fluorides can be efficiently generated in
situ from the corresponding ammonium hydrogensulfates by stirring with excess amount of
potassium fluoride in THF at ambient temperature, and directly used as a fluoride source for the
generation of carbon nucleophiles from organosilicon compounds. This method based on the anion
exchange under solid-liquid phase-transfer conditions can be successfully applied to the
preparation of C 2 -symmetrid chiral quaternary ammonium fluorides, which smoothly catalyze the
enantioselective Mukaiyama-type aldol reactions under mild conditions. The present approach can
liberate us from the troublesome synthesis and purification of anhydrous ammonium fluorides, and
thus enable rationa molecular design and preparation of effectie chiral quaternary ammonium
fluorides for asymmetric synthesis.
23

Paper: 90004141
Symposium: 60: Phase-Transfer Catalysis
Hotel: Hilton Hawaiian Village - Tapa
Room: Iolani VII
Day: Saturday PM
Time: 1:00
Invited: N
Poster
Introduction:
Chain-growth Polycondensation in Water-Organic Solvent System with Phase Transfer
Catalyst. Mr. Norihiko Hiyama, Professor Shuiti Hiraoka, Professor Tsutomu Yokozawa.
Kanagawa University, Applied Chemistry, 3-27-1 Rokkakubashi, Kanagawa-ku, Yokohama,
Kanagawa, Japan, 81-045-491-7915, yoklab1@cc.kanagawa-u.ac.jp. We have been studying
chain-growth polycondensation that proceeds from an initiator via chain polymerization manner
yielding condensation polymers with controlled molecular weights and narrow molecular weight
distributions (MWD). It has been recently reported that 4-bromomethyl-2-n-octyloxybenzoic acid
potassium salt (1) undergoes chain-growth polycondensation in solid-organic solvent system with
18-crown-6 ether as a phase transfer catalyst (PTC) in the presence of 4-nitrobenzyl bromide (2)
as an initiator. In this paper, we report the polymerization of 1 in water-organic solvent system
with (PTC) in the presence of 2. In the polymerization of 1 with tetra-n-butylammonium bromide
and 2 in water-dichloromethane, polymers with controlled molecular weights against the ratio of
1/2 were obtained, but MWDs were broad. On the basis of the observation of polymer both
terminal groups at each conversion, step polymerization was found to be contained in this system
24

Paper: 67303510
Symposium: 60: Phase-Transfer Catalysis
Hotel: Hilton Hawaiian Village - Tapa
Room: Iolani VII
Day: Saturday PM
Time: 1:00
Invited: N
Poster
Introduction:
Synthesis of Polymer-immobilized Heteropoly Acids A? PTC Complex and Its Catalytic
Activity. Dr. Takashi Iizawa, Mr. Tatsuya Asai. Hiroshima University, 1-4-1 Kagamiyama,
Higashi-Hiroshima, Hiroshima, Japan, 81-824-22-7191, tiizawa@ipc.hiroshima-u.ac.jp. Heteropoly
acids - phase transfer catalyst (PTC) complex [Na 3 PW 12 O 40 - cetylpyridinium chloride (CPC)] is
well known as a catalyst for selective epoxidation of alkene and oxidation of secondary alcohol
under mild conditions. We design novel heteropoly acids A? CPC complex immobilized by
acrylamide gels. The polymer-immobilized catalyst was prepared by reversed phase suspension
polymerization of aqueous N,N-dialkylacrylamide or acrylamide solution with heteropoly acids and
crosslinker in cyclohexane, followed by the reaction of the resulting beads with CPC in water. The
oxidation of secondary alcohol with aqueous hydrogen peroxide solution was carried out using the
polymer-immobilized catalyst at 60?C. The oxidation proceeded smoothly to give the
corresponding ketone. The polymer-immobilized heteropoly acids A? CPC complex showed higher
catalytic acitivity, compared with the corresponding low molecular weight catalyst and polymer-supported
heteropoly acids A? CPC complex. In addition, the decrease of catalytic activity was
hardly observed in the reaction
25

Paper: 90001728
Symposium: 60: Phase-Transfer Catalysis
Hotel: Hilton Hawaiian Village - Tapa
Room: Iolani VII
Day: Saturday PM
Time: 1:00
Invited: N
Poster
Introduction:
Asymmetric a a-alkylation of amino esters and peptides using chiral pyridoxal model
compounds having an ionophore function. Mr. Hiroshi Iwaki, Dr. Kazuyuki Miyashita, Mr.
Kuninori Tai, Ms. Naoko Sasaki, Professor Takeshi Imanishi. Osaka University, Graduate School of
Pharmaceutical Sciences, 1-6 Yamadaoka, Suita, Osaka, Japan, 81-6-6879-8204,
iwaki@phs.osaka-u.ac.jp. We designed novel pyridoxal model compounds having a chiral
ionophore function and/or a chiral ansa-structure and applied them to ?-alkylation of ?-amino
esters. Asymmetric ?-alkylation of amino esters was achieved by the following reaction systems:
1) a combination of the pyridoxal derivative having a chiral ionophore side chain and Na+; 2) a
combination of the pyridoxal derivative having a chiral ansa-structure and an ethoxyethoxy group
and Li+. Double asymmetric induction effect was also observed by employing the compound
having both chiral elements, the chiral ionophore side chain and the chiral ansa-structure. Upon
applying the pyridoxal derivative having a chira ansa-structure to peptides, N-terminal selective
and stereoselective ?-alkylation of peptides was successfully achieved and the stereoselectivity of
the reaction was found to depend on the chirality of the pyridoxal derivative and the reaction
conditions, not on the chirality of the peptides.
26

Paper: 90008704
Symposium: 60: Phase-Transfer Catalysis
Hotel: Hilton Hawaiian Village - Tapa
Room: Iolani VII
Day: Saturday PM
Time: 1:00
Invited: N
Poster
Introduction:
The synthses and application of N(9)-o(m, or p)-benzyldicinchonidinium bromide..
Professor Sang-Sup Jew, Mr. Byeong-Seon Jung, Ms. Misuk You, Mr. Mi-Kyoung Park, Mr. Dong-Hwa
Kim, Professor Hyeung-Geun Park. Seoul National University, College of Pharmacy, San 56-1,
Sinllim-Dong, Kwanak-gu, Seoul, South Korea, +82-2-886-7621, ssjew@plaza.snu.ac.kr. Since the
pioneering work of O'Donnell et al, the enantioselective alkylation of prochiral protected glycin
derivative using chiral phase transfer catalyst, cinchona alkaloid has been very attractive method
for the preparation of both natural and unnatural amino acids. Recently, Lygo's group and Corey's
group reported independently the highly enantioselective synthetic method for amino acid using
cinchona alkaloid derivative, N(9)-antracenylmethylcinchonidinium bromide. Also Maruoka's group
developed very efficient noncinchona type alkolid catalyst, C 2 -symmetrical chiral quaternary
ammonium salt prepared from (S)-binaphthol. Recently, we developed novel C 2 symmetric N(9)-o
(m, or p)-benzyldicinchonidinium bromide. Here we reported the preparation and the application of
C 2 -symmetrical cinchona alkaloid derivatives to prepare amino acid.
27

Paper: 90009937
Symposium: 60: Phase-Transfer Catalysis
Hotel: Hilton Hawaiian Village - Tapa
Room: Iolani VII
Day: Saturday PM
Time: 1:00
Invited: N
Poster
Introduction:
Asymetric Michael reaction utilizing chiral quaternary ammonium salt under phase-transfer
catalyzed conditions. Ms. Kimiko Katayama, Professor T. Shioiri, Dr. S. Arai.
Nagoya City University, Pharmaceutical Sciences, 3-1 Tanabe-dori, Nagoya, Aichi, Japan, 81-52-
834-4172, p953018@phar.nagoya-cu.ac.jp. Graphics
28

Paper: 90005470
Symposium: 60: Phase-Transfer Catalysis
Hotel: Hilton Hawaiian Village - Tapa
Room: Iolani VII
Day: Saturday PM
Time: 1:00
Invited: N
Poster
Introduction:
The Julia -Colonna asymmetric epoxidation reaction of benzalacetophenone catalyzed by
soluble oligo-l-leucines. Mr. Toshiki Manabe, Dr. Ryukichi Takagi, Dr. Satoshi Kojima,
Professor Katsuo Ohkata. Hiroshima University, Department of Chemistry, Graduate School of
Science, Hiroshima University, 1-3-1 Kagaiyama , Higashi-Hiroshima, Hiroshima, Japan, 81-0824-24-
0747, m1174022@hiroshima-u.ac.jp. The Julia -Colonna reaction, which utilizes solid oligo-L-leucine
catalysts, has emerged as a highly efficient method for asymmetric epoxidation of electron-deficient
olefins such as benzalacetophenone. However, the insolubility of the catalyst in ordinary
oraganic solvents has hampered mechanistic examinations. By taking advantage of the great
solubility of peptides containing an ?-aminoisobutyric acid (Aib) residue, we have prepared length-defined
soluble oligo-L-leucines containing an Aib residue by fragment condensation methods, and
have used them as catalysts in the epoxidation reaction. The yields and enantioselectivities rose by
increasing the number of amino acid units in the catalyst with values up to 73% yield and 94%
e.e., respectively, which are comparable with those obtained with conventional insoluble catalysts.
The IR characteristic bands (amide I region) in CH 2 Cl 2 and CD spectrum in CF 3 CH 2 OH indicated
the soluble catalysts to be of helical structure in solution.
29

Paper: 90001736
Symposium: 60: Phase-Transfer Catalysis
Hotel: Hilton Hawaiian Village - Tapa
Room: Iolani VII
Day: Saturday PM
Time: 1:00
Invited: N
Poster
Introduction:
b b-Replacement reaction of serine derivertives using pyridoxal model compounds having
an ionophore function. Dr. Kazuyuki Miyashita, Mr. Hiroshi Iwaki, Mr. Hidenobu Murafuji, Ms.
Naoko Sasaki, Professor Takeshi Imanishi. Osaka University, Graduate School of Pharmaceutical
Sciences, 1-6 Yamadaoka, Suita, Osaka, Japan, 81-6-6879-8201, miyasita@phs.osaka-u.ac.jp. We
focused on ?-replacement reaction of serine as one of reactions mediated by pyridoxal in a
biological system and studied its application to the synthesis of unnatural amino acids and peptides
by employing pyridoxal model compounds having an ionophore function. The reaction of serine O-carbonate
with aryl mercaptans smoothly took place to afford S-aryl cysteine derivatives only in
the presence of a catalytic amount of Li + and the model compound having an ethoxyethoxy group
at C-3. Although the reaction with alkyl mercaptans proceeded only in lower yields, this problem
was resolved by using the model compound having an additional basic residue at C-5. Furthermore
the model compound having a methylthio group at C-2, which had been designed to have a
heterobimetal chelation ability, successfully catalyzed the reaction with carbon nucleophiles in the
presence of Li + and Zn 2+ .
30

Paper: 81297130
Symposium: 60: Phase-Transfer Catalysis
Hotel: Hilton Hawaiian Village - Tapa
Room: Iolani VII
Day: Saturday PM
Time: 1:00
Invited: N
Poster
Introduction:
Microemulsion Phase Formed in the Quaternary Salt / Oil / Water / Inorganic Salt Four-Component
Systems and Its Role to Phase-Transfer Catalysis.. Dr. Noritaka Ohtani, Mr.
Yasuhiro Hosoda, Mr. Daisuke Tsuchimoto, Mr. Tsuyoshi Yamashita. Department of Materials
Engineering and Applied Chemistry for Environments, Faculty of Engineering and Resource
Science, Akita U, Akita, Akita, Japan, 81-18-837-0404, ohtani@ipc.akita-u.ac.jp. The phase
behavior of the four-component systems, composed of quaternary salt (QX), nonpolar oil, water,
and metal halide (MX), has been examined. According to their constituent, composition, and
temperature, the systems afforded from single- to four-phase state. There were at least three kind
of liquid phases; a quat-rich phase (M), an aqueous solution phase (W), and an oil solution phase
(O). In the M phase, QX was assumed to form aggregates like microemulsions based on the
solubility and NMR analyses, while, in the latter two solution phases, QX was present without any
aggregated form. When these three liquid phases coexist, an O-M-W three-liquid-phase equilibrium
state occurred. Depending on temperature and MX concentration in W phase, the system changed
its state. A solid MX phase (S) often coexisted with these liquid phases, leading to the formation of
an O-M-W-S four-phase state. These phase separation phenomena were compared with the PTC
activity about some nuclephilic substitutions.
31

Paper: 90001505
Symposium: 60: Phase-Transfer Catalysis
Hotel: Hilton Hawaiian Village - Tapa
Room: Iolani VII
Day: Saturday PM
Time: 1:00
Invited: N
Poster
Introduction:
Formation of salt-free ylides and active sulfur by using TDA-1. Professor Kentaro
Okuma. Fukuoka University, Chemistry, Nanakuma, Jonan-ku, Fukuoka, Fukuoka, Japan, 81-92-865-
6030, kokuma@fukuoka-u.ac.jp. Salt-free phosphorus ylides were obtained by the reaction
of phosphonium salts with NaH in the presence of tris[2-(2-methoxyethoxy)ethyl]amine (TDA-1)
as a phase transfer catalyst. The formation of ylides was confirmed by the reaction with
aldehydes, which resulted in the formation of olefins with Z-stereoselectivity. Active sulfur was
also obtained by the reaction of elemental sulfur with 5 % molar amount of NaH in the presence
of TDA-1 as a phase-transfer catalyst.
32

Paper: 90001494
Symposium: 60: Phase-Transfer Catalysis
Hotel: Hilton Hawaiian Village - Tapa
Room: Iolani VII
Day: Saturday PM
Time: 1:00
Invited: N
Poster
Introduction:
Oxidation of sulfides to sulfoxides and sulfones with 30% hydrogen peroxide under
organic solvent- and halogen-free conditions. Dr. Kazuhiko Sato, Mr. Mamoru Hyodo, Dr.
Masao Aoki, Dr. Xiao-Qi Zheng, Professor Ryoji Noyori. Nagoya University, Department of
chemistry and research center for materials science, Chikusa, Nagoya, Aichi , Japan, 81-52-783-4177,
sato@chem3.chem.nagoya-u.ac.jp. Aromatic and aliphatic sulfides are oxidized to sulfoxides
or sulfones in high yield with 30% hydrogen peroxide under organic solvent- and halogen-free
conditions. Dialkyl and alkyl aryl sulfides are cleanly oxidized to the sulfoxides with aqueous
hydrogen peroxide without catalysts. The best catalyst for the sulfone synthesis consists of sodium
tungstate, phenylphosphonic acid, and methyltrioctylammonium hydrogensulfate. Co-existing
primary or secondary alcohol or olefinic moieties are unaffected under such conditions.
33

Paper: 62926950
Symposium: 60: Phase-Transfer Catalysis
Hotel: Hilton Hawaiian Village - Tapa
Room: Iolani VII
Day: Saturday PM
Time: 1:00
Invited: N
Poster
Introduction:
Azacrown ethers that possess the glucose moiety and their catalytic properties for the
asymmetric phase transfer catalyst. Mr. Shohei Shirakami, Professor Toshiyuki Itoh. 3-1-1
Tsushima-naka, Okayama City, Okayama, Japan, 81-86-251-7639, titoh@cc.okayama-u.ac.jp.
Several types of novel azacrown ethers that contain the glucose moiety have been synthesized
and their catalytic properties on the asymmetric Michael reaction or substitution reaction have
been investigated.
34

Paper: 90010017
Symposium: 60: Phase-Transfer Catalysis
Hotel: Hilton Hawaiian Village - Tapa
Room: Iolani VII
Day: Saturday PM
Time: 1:00
Invited: N
Poster
Introduction:
Development of asymmetric Darzens reaction utilizing phase-transfer catalyst. Ms.
Yukari Suzuki, Professor Takayuki Shioiri, Dr. Shigeru Arai. Nagoya City University,
Pharmaceutical Sciences, 3-1 Tanabe-dori, Mizuho-ku, Nagoya, Aichi, Japan, 81-52-834-4172,
p95303@phar.nagoya-cu.ac.jp. Graphics
35

Paper: 90003974
Symposium: 60: Phase-Transfer Catalysis
Hotel: Hilton Hawaiian Village - Tapa
Room: Iolani VII
Day: Saturday PM
Time: 1:00
Invited: N
Poster
Introduction:
Crown ether - carboxylic acid conjugates as new receptors for bifunctional amino acids.
Professor Hiroshi Tsukube, Mr. Hiroshi Fukui, Mr. Yoshihisa Mizutani, Dr. Satoshi Shinoda.
Osaka City University, Department of Chemistry, Graduate School of Science, 3-3-138 Sugimoto,
Sumiyoshi-ku, Osaka, Osaka, Japan, 81-6-6605-2522, tsukube@sci.osaka-cu.ac.jp. Amino acids
are one of the most important substrates both in biological and artificial processes. Since they are
hydrophilic and bifunctional species, artificial receptors should have multiple binding sites
complementary for amine and carboxylic acid sites of the amino acid substrate [1]. Here, we
present a novel type of ditropic receptors effective for the bifunctional amino acids in which benzo-18-
crown-6 moiety is connected with ferrocenecarboxylic acid. In this system, the ferrocene acts
as "molecular bearing" to adjust the locations of crown ring and carboxylic acid for cooperative
binding of bifunctional amino acids. Liquid-liquid extraction and FAB-MS binding experiments
revealed that several amino acids were effectively extracted from the acidic aqueous solution via
1 : 1 complexation with this conjugate. [1] H.Tsukube, M.Wada, S.Shinoda and H.Tamiaki, Chem.
Commun., 1007 (1999).
36

Paper: 55444060
Symposium: 60: Phase-Transfer Catalysis
Hotel: Hilton Hawaiian Village - Tapa
Room: Iolani VII
Day: Saturday PM
Time: 1:00
Invited: N
Poster
Introduction:
N-ALKYLATION OF 2-MERCAPTOBENZIMIDAZOLE DERIVATIVES UNDER PHASE-TRANSFER
CATALYTIC CONDITIONS. Professor Maw-Ling Wang, Mr. Wei-Wen Chen, Mr.
Wei-Wen Chen. Natl Chung Cheng Univ, 160 SAN-HSIN VILLAGE, CHIAYI, TAIWAN, USA, 886-05-272-
0404, chmmlw@ccunix.ccu.edu.tw. N-alkylation of 2-mercaptobenzimidazole (MBI)derivatives
with allyl bromide in KOH/organic solvent two-phase medium was carried out via phase-transfer
catalysis. In a high KOH concentration, N-alkylation of MBI takes place on nitrogen atom. Kinetics
dominates the reaction even in a low agitation speed. Effects of reaction conditions on conversion
are investigated in detail. The reaction is enhanced by catalyst, allyl bromide and KOH. However,
the conversion is decreased with the increase in the amount of MBI derivatives, and is insensitive
to the amount of water. The order of the reactivity for these catalysts are: TBAB > BTEAB >
CTMAB > Tween 80, and for these organic solvents are: dichloromethane > 1,2-dichloroethane >
chloroform > chlorobenzene > carbon tetrachloride. The reaction is also enhanced by adding
potassium carbonate in which the confirmation of reaction is catalyzed by amine hydrochloride.
The reaction is identified as the Brandstrom-Montanari mechanism.
37

Paper: 68667260
Symposium: 60: Phase-Transfer Catalysis
Hotel: Hilton Hawaiian Village - Tapa
Room: Iolani VII
Day: Saturday PM
Time: 1:00
Invited: N
Poster
Introduction:
The Multiphase Catalytic Hydrodechlorination as a Useful Tool for the Detoxification of
Hazardous Organic Pollutants. Mr. Sergei Zinovyev S, Professor Pietro Tundo, Dr. Stefano
Raccanelli, Dr. Alvise Perosa. Leninsky pr. 47, Moscow, Moscow, Russia, +07 (095) 1355328,
zinovev@ufn.ioc.ac.ru, sergei@unive.it. A new catalytic system consisting of a hydrogen solvent
and an aqueous phase, and catalyzed by a metal-supported catalyst coupled with a phase-transfer
agent, allows the rapid and efficient hydrodedechlorination of various polychlorinated and other
substituted aromatics. The reaction proceeds with hydrogen at atmospheric pressure and at 50?C
and affords the quantitative yields of reduction products. The applicability of this mild technique to
the degradation of PCBs and a number of toxic 2,3,7,8-tetra and higher polychlorinated dibenzo-p-dioxins
and dibenzofurans, collected from a waste incinerator was demonstrated. The results were
also compared to those, obtained for the hydrodechlorination in a normal catalytic system where
various polychlorinated benzenes and PCB were also reduced on different metal-supported
catalysts using different sources of hydrogen. The multiphase system is shown to be a promising
environmentally friendly tool for the detoxification of hazardous organic wastes and a convenient
experimental technique for the selective reduction of other functional groups as well.
38