Synthesis of alkylammonium tosylates with poly{[4-hydroxy(tosyloxy)iodo] styrene}

Article abstract of DOI:10.1081/SCC-200050954

Several primary carboxamides (RCONH₂) were converted to the corresponding alkylammonium tosylates (RN⁺H₃ ^-OTs) with poly{[4-hydroxy (tosyloxy) iodo]styrene} (PSHTIB) in yields ranging from 60% to 90%.

Full text of DOI:10.1081/SCC-200050954

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Synthesis of Alkylammonium Tosylates with
Poly{[4‐Hydroxy(Tosyloxy)Iodo]Styrene}
Shi Juan Liu a , Ji Zhen Zhang a b , Guan Rong Tian a & Ping Liu a
a Department of Chemistry , Yan Bian University , Yan Ji City, Ji Lin, China
b Chemistry and Chemical Engineering Department , Jiang Su Teachers
University of Technology , Chang Zhou City, Jiang Su, China
Published online: 20 Aug 2006.
To cite this article: Shi Juan Liu , Ji Zhen Zhang , Guan Rong Tian & Ping Liu (2005) Synthesis of
Alkylammonium Tosylates with Poly{[4‐Hydroxy(Tosyloxy)Iodo]Styrene}, Synthetic Communications: An
International Journal for Rapid Communication of Synthetic Organic Chemistry, 35:6, 823-827, DOI: 10.1081/
SCC-200050954
To link to this article: http://dx.doi.org/10.1081/SCC-200050954
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Synthetic Communicationsw, 35: 823–827, 2005
Copyright # Taylor & Francis, Inc.
ISSN 0039-7911 print/1532-2432 online
DOI: 10.1081/SCC-200050954
Synthesis of Alkylammonium Tosylates with
Polyf[4-Hydroxy(Tosyloxy)Iodo]Styreneg
Shi Juan Liu
Department of Chemistry, Yan Bian University, Yan Ji City, Ji Lin, China
Ji Zhen Zhang
Chemistry and Chemical Engineering Department, Jiang Su Teachers
University of Technology, Chang Zhou City, Jiang Su, China and
Department of Chemistry, Yan Bian University, Yan Ji City, Ji Lin, China
Guan Rong Tian and Ping Liu
Department of Chemistry, Yan Bian University, Yan Ji City, Ji Lin, China
Abstract: Several primary carboxamides (RCONH2) were converted to the corre-
sponding alkylammonium tosylates (RNþH32OTs) with polyf[4-hydroxy (tosyloxy)
iodo]styreneg (PSHTIB) in yields ranging from 60% to 90%.
Keywords: Alkylammonium tosylate, carboxamide, Hofmann rearrangement,
polyf[4-hydroxy(tosyloxy)iodo]styreneg
Applying hypervalent iodine reagents in the synthetic processes could avoid
the use of toxic compounds containing heavy metals, such as lead, mercury,
and chromium. Generally, the reaction conditions are exceedingly simple,
especially without special precautions to the solvents for the exclusion of
oxygen or humidity. Moreover, polymer-supported hypervalent iodine
reagents also provided simplicity of workup. Thus, polymer-supported hyper-
valent iodine reagents have been intensively applied in various synthesis.[1]
Received in Japan October 13, 2004
Address correspondence to Guan Rong Tian, Department of Chemistry, Yan Bian
University, Yan Ji City, Ji Lin 133002, China. E-mail: grtn@ybu.edu.cn

824
S. J. Liu et al.
Polyf[4-Hydroxy(Tosyloxy)Iodo]Styreneg (PSHTIB) as a polymer-
supported reagent was found to have the same properties as [hydroxyl
(tosyloxy)iodo]benzene (HTIB). It is a readily available and stable crystalline
compound, which can be handled under ambient conditions.[2] Gerald F.
Koser reported aliphatic carboxamides converted to alkylammonium
tosylates with HTIB.[3] We have explored the utility of PSHTIB as a
Hofmann reagent, and the results of the study are described in this
communication.
PSHTIB was prepared from the commercial linear polystyrene (average
MW ¼ 250,000) by the reported method.[2,4] The exact loading capacity of
PSHTIB was 1.91 mmol/g, which was measured by element analysis
(Scheme 1).
When PSHTIB was mixed with primary carboxamide in acetonitrile, the
reaction took place at reflux. After the reaction, the mixtures were hot-
filtrated. Then, they were kept below 108C and the corresponding alkylammo-
nium tosylates were separated. Iodinated polystyrene was recovered by
simple filtration and was converted to PSHTIB according to the reported
method.[2,4] The loading capacity of the reagent was 1.88 mmol/g. We
used this reagent with the propionamide and got good results. This result
showed the reagent had almost the same functional group as the original
prepared reagent (Table 1).
Hexylammonium tosylate. White powder, IR (KBr): 3433, 1490, 1189,
1
817 cm21; H NMR (d, CDCl3, 300 MHz): 0.80 (t, J ¼ 6.3 Hz, 3H), 1.11
(m, 6H), 1.40 (m, 2H), 2.36 (s, 3H), 2.72 (m, 2H), 7.20 (d, 2H, J ¼ 8 Hz),
7.70 (s, 3H), 7.98 (d, 2H, J ¼ 8 Hz). 13C NMR (d CDCl3, 75 MHz): 13.89,
21.29, 22.33, 25.99, 27.36, 31.08, 39.33, 125.90, 128.99, 140.70, 141.26.
Anal. calcd. for C13H23NO3S: C, 57.11; H, 8.48; N, 5.12. Found: C, 57.04;
H, 8.57; N, 4.94.
Heptadecylammonium tosylate. White powder, IR (KBr): 3432, 1470,
1
1189, 817 cm21, H NMR (d, CDCl3, 300 MHz): 0.90 (t, J ¼ 6.9 Hz), 1.15–
1.49 (m, 30H), 2.37 (s, 3H), 2.75 (s, 2H), 7.17 (d, J ¼ 7.9 Hz, 2H), 7.60
(s, 3H), 7.75 (d, J ¼ 7.9 Hz, 2H). 13C NMR (d CDCl3, 75 MHz): 14.08,
21.30, 22.67, 24.75, 26.38, 27.45, 29.01, 29.34, 29.43, 29.59, 29.71, 31.91,
39.92, 110.13, 125.91, 129.00, 140.68, 141.24. Anal. calcd. for
C24H45NO3S: C, 67.40; H, 10.61; N, 3.27. Found: C, 67.57; H, 10.67; N, 2.99.
Naphthylmethylammonium tosylate. White powder, IR (KBr): 3436,
1
1182, 814 cm21; H NMR (d, DMSO, 300 MHz): 2.35 (s, 3H), 4.20–4.55
Scheme 1.

Table 1. Results for the Hofmann reactions
Mp (8C)
Yields (%)
PSHTIB
R
Reflux (h)
Productsb
CH3NþH23 OTs
Found
Lit.
HTIB
Me
Et
12
2
142–143
115–116
133–134
114–117
127–129
102–115
72–78
146–147[5]
118[5]
82
93
90
CH3CH2 NþH23 OTs
CH3(CH2)2 NþH32OTs
CH3(CH2)5 NþH32OTs
CH3(CH2)6 NþH32OTs
CH3(CH2)10 NþH32OTs
CH3(CH2)16 NþH32OTs
PhCH2 NþH23 OTs
89 (87a)
60
82
n-Pr
1
139[5]
n-Hex
n-Hep
n-Und
n-Ole
Benzyl
C10H7CH2
3
3
131–133[3]
102–130[3]
70
70
93
57
1
2
89
90
3
177–180
170–177
185.5[5]
89
3
C10H7CH2 NþH23 OTs
88
aBy applying polyf[4-hydroxy(tosyloxy)iodo]styreneg recycled.
1
bIR, H NMR spectra were identical with the literature.

826
S. J. Liu et al.
(q, J ¼ 5.6 Hz, 2H), 7.10ꢀ8.16 (m, 11H), 8.28 (s, 3H). 13C NMR (d, DMSO,
75 MHz): 21.22, 43.00, 123.89, 125.83, 125.96, 126.75, 127.23, 127.76,
128.48, 129.15, 129.64, 130.37, 131.12, 133.72, 138.00, 146.29. Anal.
calcd. for C18H19NO3S: C, 65.63; H, 5.81; N, 4.25. Found: C, 65.21; H,
5.63; N, 4.12.
CONCLUSIONS
Several alkylammonium tosylates (RNþH32OTs) were obtained from corre-
sponding primary carboxamides (RCONH2) with PSHTIB in acetonitrile at
reflux. The reaction is mild and has operational simplicity, good yields, and
the possibility of recycling, according with green chemistry’s requirement.
ACKNOWLEDGMENT
This work was supported by the grants from the Science and Technology
Committee of Ji Lin Province, China.
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