Synthesis, characterization, and utility of trialkyl(3-sulfopropyl)ammonium betaines as new phase transfer reagents

Article abstract of DOI:10.1081/SCC-120021835

Synthesis of water-soluble phase transfer reagents, trialkyl(3-sulfopropyl)ammonium betaines and its utility in various hydroxide-ion initiated reactions are described.

Full text of DOI:10.1081/SCC-120021835

Synthetic Communications
An International Journal for Rapid Communication of Synthetic Organic
Chemistry
ISSN: 0039-7911 (Print) 1532-2432 (Online) Journal homepage: http://www.tandfonline.com/loi/lsyc20
Synthesis, Characterization, and Utility of
Trialkyl(3-sulfopropyl)ammonium Betaines as New
Phase Transfer Reagents
Joseph Paul Jayachandran & Maw-Ling Wang
To cite this article: Joseph Paul Jayachandran & Maw-Ling Wang (2003) Synthesis,
Characterization, and Utility of Trialkyl(3-sulfopropyl)ammonium Betaines as New Phase
Transfer Reagents, Synthetic Communications, 33:14, 2463-2468, DOI: 10.1081/SCC-120021835
To link to this article: http://dx.doi.org/10.1081/SCC-120021835
Published online: 20 Aug 2006.
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SYNTHETIC COMMUNICATIONSÕ
Vol. 33, No. 14, pp. 2463–2468, 2003
Synthesis, Characterization, and Utility of
Trialkyl(3-sulfopropyl)ammonium Betaines as
New Phase Transfer Reagents
Joseph Paul Jayachandran1 and Maw-Ling Wang2,
*
1Department of Chemical Engineering, National Chung
Cheng University, Chiayi, Taiwan, R.O.C.
2Department of Chemical Engineering, Tung Hai
University Taichung, Taiwan, R.O.C.
ABSTRACT
Synthesis of water-soluble phase transfer reagents, trialkyl(3-sulfo-
propyl)ammonium betaines and its utility in various hydroxide-ion
initiated reactions are described.
Phase Transfer Catalysis (PTC) is connected with conversions
between chemical species situated in different phases (aqueous/
organic).[1–3] Common cases are reaction between, on the hand, salts
dissolved in water or present in solid phase, and on the other, substances,
dissolved in organic media. The advantages of PTC method over con-
ventional methods are increased rates of reaction, increased product
*Correspondence: Maw-Ling Wang, Department of Chemical Engineering,
Tung Hai University Taichung, Taiwan, 407, R.O.C.
2463
DOI: 10.1081/SCC-120021835
Copyright & 2003 by Marcel Dekker, Inc.
0039-7911 (Print); 1532-2432 (Online)
www.dekker.com

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2464
Jayachandran and Wang
specificity, lower energy requirements, commercially available inexpen-
sive catalysts, use of inexpensive non-toxic, recoverable solvents or use
of liquid reactant as a solvent, use of inexpensive bases for anion gen-
eration, use of inexpensive oxidants, reduced cycle time and pollution
prevention.
The nucleophilic ring opening of 1, 3-propanesultone by tertiary
amines readily leads to sulfopropylbetaine type compounds. A brief lit-
erature survey[4–9] reveals that sulfobetaine monomers were considered as
functional monomers and finds applicability as minor components for
copolymers in various fields like synthetic textile fibres, hydrophilic and
charged dispersing agents and protective colloids.
This communication deals with the synthesis of triethyl(3-sulfopro-
pyl)ammonium betaine[QS-1] and tributyl(3-sulfopropyl)ammonium
betaine [QS-2] and report its utility in hydroxide-ion initiated reactions
as a new phase transfer reagent.
The synthesis of QS-1 and QS-2 as a new phase transfer reagents are
described in Sch. 1. Quaternizations were performed at 75ꢀC, using a
stoichiometric ratio [propanesultone]/[amine] ¼ 1.1 in the presence of an
aprotic solvent, acetonitrile where the trialkyl(3-sulfopropyl)ammonium
betaines are insoluble. Catalytic amount of 1,3-dinitrobenzene (1,3-DNB)
is used as a free radical polymerization inhibitor in the present reaction.
In order to investigate the efficiency of the new phase transfer
reagents under study, dichlorocarbene addition to different olefins have
been chosen. The results shown in Table 1 establish the utility of
trialkyl(3-sulfopropyl)ammonium betaines (QS-1 and QS-2) for the
dichlorocyclopropanation reactions. In the absence of the phase transfer
reagent less than 1% conversion is detected (even after 3 h of reaction) by
gas chromatography. Excellent yields of products were obtained in 2 h
on using 1 mol% (based on the substrate amount) of the new catalyst
Et
_
3
+
Et
N
SO
QS-1
QS-2
Et
..
Et N or Bu N
..
1, 3 - DNB, CH3CN, 75°C
or
+
3
3
O
S
Bu
O
O
_
3
+
Bu
SO
N
Et = Ethyl; Bu = Butyl
Bu
Scheme 1.

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Phase Transfer Reagents
2465
Table 1. Dichlorocarbene addition to different olefins using QS-1 and QS-2.
% Conversiona
Entry
1
Substrate
Product
QS-1
85
QS-2
88
Cl
Cl
2
3
90
89
92
90
Cl
Cl
Cl
Cl
4
5
93
70
90
72
Cl
Cl
Cl
Cl
_
_
6
7
CH3-(CH2)2ꢁCH¼CH2
CH3-(CH2)5ꢁCH¼CH2
93
89
90
91
CH
(CH )
CH
CH
2
2
3
2
Cl
Cl
_
_
CH2
Cl
CH
(CH2)
5 CH
Cl
CH3
_
3
_
8
CH3-(CH2)7ꢁCH¼CH2
CH3-(CH2)9ꢁCH¼CH2
86
90
(CH )
2
CH
7
CH
2
Cl
Cl
_
3
_
9
9
85
98
87
96
CH
(CH )
CH
CH
2
2
Cl
Cl
Cl
10
Cl
Cl
11
12
90
75
88
79
Cl
CH Cl
2
CH Cl
2
O
O
_
_
_
_
CH2
O CH
CH
2
C
O CH
C
Cl Cl
a% conversion by gas chromatography.

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2466
Jayachandran and Wang
thus revealing the remarkable efficiency of trialkyl(3-sulfopropyl)ammo-
nium betaines as potential phase transfer reagents.
EXPERIMENTAL
General
1H NMR (400 MHz) was recorded on a BRUKER-AM-400 NMR
Spectrometer with TMS as an internal standard. The infrared spectra
were measured on a PERKIN-ELMER model 983 IR Spectrometer.
Gas Chromatography was carried out using Shimadzu SC-14B instrument.
Synthesis of Triethyl(3-sulfopropyl)ammonium Betaine [QS-1]
and Tributyl(3-sulfopropyl)ammonium Betaine [QS-2]
The reagents, QS-1 and QS-2 were prepared according to the litera-
ture procedure described elsewhere.[4,9] 1, 3-Propanesultone (1.2 g,
0.001 mol) was dissolved in dry acetonitrile (20 mL) and transferred
into a 150 mL two-necked flask. The solution was deaerated and
1.3 mL (0.001 mol) triethylamine (for QS-1) or 2.4 mL (0.001 mol) tri-
butylamine (for QS-2) was added to the solution. 0.001 g (0.0006 mol)
of 1, 3- dinitrobenzene was added to the reaction mixture, which is
used as a free radical polymerization inhibitor in the process. The reac-
tion stirred under gentle refluxing condition at 75ꢀC for 7 h under nitro-
gen atmosphere. To the cold reaction mixture 20 mL diethyl ether was
added and a precipitate was collected (90% yield) and filtered repeatedly
washed with ether (3 times). The white, solid QS-1 or QS-2 (highly hygro-
scopic) was stored in a CaCl2 desiccator. QS-1: 1H NMR (400 MHz,
CDCl3): ꢀ ¼ 3.68 (t, 2H, -CH2), 3.54 (t, 2H, CH2), 3.12 (t, 2H, -CH2),
2.82 (q, 2H, -CH2), 2.15 (q, 2H, -CH2), 1.65(q, 2H, -CH2), 1.26–1.13 (m,
6H, -CH3), 0.82 (t, 3H, -CH3). ꢁmax/cmꢁ1: 2926, 2208, 1649, 1486, 1378,
980, 803. QS-2: 1H NMR (400 MHz, CDCl3): ꢀ ¼ 4.26 (t, 2H, -CH2), 3.67
(t, 2H, -CH2), 3.41–3.17 (m, 8H, -CH2), 2.85 (t, 2H, -CH2), 2.19
(t, 2H, -CH2), 1.68 (t, 2H, -CH2), 1.30–1.28 (m, 12H, -CH2, CH3),
0.86–0.82 (t, 3H, -CH3). ꢁmax/cmꢁ1: 2924, 2080, 1644, 1207, 1042, 980,
805.

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Phase Transfer Reagents
General Procedure for the Dichlorocarbene Addition
2467
to Olefins Using the New Phase Transfer Reagents,
QS-1 and QS-2
The 150 mL three-necked round bottomed flask was charged with
20 mL (40% w/w) NaOH, 1 mol% of the phase transfer reagent (based
on the substrate amount) [QS-1 or QS-2] and chloroform (20 mL). The
ingredients were conditioned for 10 min in the thermostat maintained at
45ꢀC. Olefin (0.5 mL) was added to the reaction mixture and stirred for
2 h at 500 rpm. The sample from the organic layer was withdrawn by a
hypodermic syringe and analyzed by Gas Chromatography (Shimadzu
GC 14B with flame ionization detector using 100% methylpolysiloxane,
dbl capillary column, 15 m ꢂ0.525 mm and nitrogen as carrier gas. To the
cold reaction mixture, ether (20 mL) was added and the ethereal layer was
washed repeatedly with water and dried over anhydrous magnesium
sulfate. The compound was purified using silica gel column chromatog-
raphy. The spectral data matched with the spectra of the authentic
samples.[10]
ACKNOWLEDGMENT
The authors thank the National Science Council, Taiwan, ROC for
the financial support under contract no. NSC87-2214-E007-012.
REFERENCES
1. Starks, C.M.; Liotta, C.L.; Halpern, M. Phase Transfer Catalysis;
Chapman & Hall: New York, 1994.
2. Dehmlow, E.V.; Dehmlow, S.S. Phase Transfer Catalysis; Verlag:
Weinheim, 1993.
3. Makosza, M.; Fedorynski, M. Polish J. of Chem. 1996, 70 (9), 1110.
4. Monroy Soto, V.M.; Galin, J.C. Polymer 1984, 25, 121.
5. Smith, J.A. Am. Chem. Soc. Polym. Prepr. 1976, 17 (2), 268.
6. Hoover, F.J. Macromol. Sci. 1970, A-4, 1327.
7. Goethals, E.J. Topics in Sulfur Chemistry 1977, 3, 3.
8. Bahr, U.; Wieden, H.; Rinkler, H.A.; Nischk, G. Makromol. Chem.
1972, 161, 1.

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2468
Jayachandran and Wang
9. Davidson, N.S.; Fetters, L.J.; Funk, W.G.; Graessley, W.W.;
Hadjichrostidis, N. Macromolecules 1988, 21, 112.
10. Jayachandran, J.P.; Wang, M.L. Synth. Commun. 1999, 29 (23),
4101.
Received in Japan August30, 2002