6176 J . Org. Chem., Vol. 66, No. 18, 2001
Notes
(KBr) 3430 (br), 2920, 1480, 1400, 1210, 1180, 1130, 1040, 1010,
820, 765, 700, 570 cm-1. Anal. Found: C, 36.33; H, 3.66.
Poly{R-methyl[4-hydroxy(tosyloxy)iodo]styrene} was prepared
under the same conditions as those described above: IR (KBr)
3440 (br), 2920, 1480, 1400, 1210, 1190, 1130, 1040, 1010, 820,
690, 570 cm-1. Anal. Found: C, 39.45; H, 4.07.
[4-(diacetoxy)iodo]styrene} and then converted to poly-
[4-hydroxy(tosyloxy)iodo]styrene and poly{R-methyl[4-
hydroxy(tosyloxy)iodo]styrene}, respectively. These re-
generated polymer reagents showed the same reactivity
that was observed in the first use with poly[4-hydroxy-
(tosyloxy)iodo]styrene and poly{R-methyl[4-hydroxy-
(tosyloxy)iodo]styrene} in the R-tosyloxylation of ketones
and oxidative R-tosyloxylation of alcohols.
Ultrasonic enhancement of R-tosyloxylation of ketones
with the present polymer reagents was not observed,
though R-tosyloxylation of ketones with [hydroxy(tosyl-
oxy)iodo]benzene was accelerated by ultrasonic irradia-
tion.8
In conclusion, poly[4-hydroxy(tosyloxy)iodo]styrene and
poly{R-methyl[4-hydroxy(tosyloxy)iodo]styrene} have
enough reactivity for the R-tosyloxylation of ketones and
the oxidative R-tosyloxylation of alcohols; moreover, these
polymer reagents can be regenerated and reused as
environmentally benign reagents.
Typ ica l P r oced u r e for r-Tosyloxyla tion of Acetop h e-
n on e. To a solution of acetophenone (0.5 mmol) and acetonitrile
(3 mL) was added poly[4-hydroxy(tosyloxy)iodo]styrene (0.401
g, 0.75 mmol). The mixture was refluxed for 3 h under an argon
atmosphere. A mixture of hexane (15 mL) and chloroform (15
mL) was added to the reaction mixture, and the solution was
filtered. The formed poly(4-iodostyrene) was recovered as a solid
quantitatively. The filtrate was evaporated, and the residue was
chromatographed on silica gel using a 4/1 mixture of hexane and
ethyl acetate as an eluent to give R-tosyloxyacetophenone.
Typ ica l P r oced u r e for Dir ect, Oxid a tive r-Tosyloxyla -
tion of r-Meth ylben zyl Alcoh ol. To a solution of R-methyl-
benzyl alcohol (0.5 mmol) in chloroform (3 mL) was added poly[4-
hydroxy(tosyloxy)iodo]styrene (0.530 g, 1.0 mmol). The mixture
was refluxed for 16 h under an argon atmosphere. A mixture of
hexane (15 mL) and chloroform (15 mL) was added to the
reaction mixture, and the solution was filtered. The formed poly-
(4-iodostyrene) was recovered as a solid quantitatively. The
filtrate was evaporated, and the residue was chromatographed
on silica gel using a 4/1 mixture of hexane and ethyl acetate as
an eluent to give R-tosyloxyacetophenone.
Exp er im en ta l Section
Gen er a l. All reactions were carried out under an argon
atmosphere. 1H NMR spectra were recorded on a 400 MHz
spectrometer. Chemical shifts are reported as parts per million
downfield from tetramethylsilane (TMS) in δ units. Values of J
are given in hertz. IR spectra were recorded on a FT/IR-200
spectrometer. Microanalyses were performed with Perkin-Elmer
240B and 240 elemental analyzers at the Chemical Analysis
Center of Tsukuba University. Melting points were determined
on a Yamato melting point apparatus in open capillary tubes
and are shown uncorrected. Silica Gel 60 (Kanto Kagaku Co.)
was used for column chromatography, Kieselgel 60 F254 (Merck)
was used for TLC, and Wakogel B-5F was used for p-TLC.
Ma ter ia ls. Polystyrene (Aldrich 33165-1), poly(R-methylsty-
rene) (Aldrich 41794-7), ketones, and most of the alcohols are
commercially available.
P r ep a r a tion of P oly[4-(d ia cetoxyiod o)styr en e]. A mix-
ture of 16 g (153 mmol) of polystyrene, 18 g (71 mmol) of iodine,
7 g (21 mmol) of iodine pentoxide, 40 mL of carbon tetrachloride,
and 35 mL of 50% sulfuric acid in 200 mL of nitrobenzene was
kept at 90 °C for 72 h. After the reactions were completed, the
reaction mixture was diluted with 100 mL of chloroform and
precipitation occurred upon the addition of methanol (1500 mL).
The precipitates were collected by filtration to give poly(4-
iodostytene). IR peaks of 700 and 760 cm-1 in polystyrene and
poly(R-methylstyrene), respectively, disappeared, and a new
peak at 820 cm-1 appeared in poly(4-iodostytene) and poly(R-
methyl-4-iodostyrene). Hydrogen peroxide (30%, 40 mL) was
added dropwise to an acetic anhydride solution (145 mL) at 0
°C. The solution was slowly warmed to room temperature and
stirred overnight. To this solution was added poly(4-iodostyrene)
(8 g). Then, the solution was kept at 48 °C overnight. At the
end of the reaction, diethyl ether was added to the solution to
cause precipitation. The product (ca. 9 g) was collected by
filtration: IR (KBr) 1630 (br), 1560 (br), 1480, 1450, 1410, 1260,
1180, 1000, 770 (br) cm-1. Anal. Found: C, 36.33; H, 3.66; I,
39.19.
r-Tosyloxya cetop h en on e: mp 90 °C (lit.4b 90-91 °C); IR
(KBr) 1715, 1360, 1180, 820, 750, 680 cm-1; 1H NMR (400 MHz,
CDCl3) 2.45 (s, 3H), 5.27 (s, 2H), 7.35 (d, J ) 8.5 Hz, 2H), 7.47
(t, J ) 8.2 Hz, 2H), 7.61 (t, J ) 7.4 Hz, 2H), 7.85 (t, J ) 7.2 Hz,
4H).
r-Tosyloxyp r op iop h en on e: mp 68 °C (lit.4b 68-69 °C); IR
(KBr) 1700, 1370, 1170, 830, 760, 660 cm-1; 1H NMR (400 MHz,
CDCl3) 1.60 (d, J ) 7.0 Hz, 3H), 2.41 (s, 3H), 5.79 (q, J ) 7.00
Hz, 1H), 7.29 (d, J ) 8.0 Hz, 2H), 7.46 (t, J ) 8.0 Hz, 2H), 7.60
(tt, J ) 7.4, 2.7 Hz, 1H), 7.75 (dt, J ) 8.5, 2.0 Hz, 2H), 7.88 (dt,
J ) 8.6, 1.3 Hz, 1H).
r-Tosyloxycycloh exa n on e: mp 72 °C (lit.4b 74-76 °C); 1H
NMR (400 MHz, CDCl3) 1.64-1.76 (m, 3H), 1.85-2.01 (m, 3H),
2.26-2.34 (m, 3H), 2.44 (s, 2H), 4.90 (ddd, J ) 10.8, 5.9, 1.0 Hz,
1H), 7.34 (d, J ) 8.0 Hz, 2H), 7.84 (d, J ) 6.5 Hz, 2H).
r-Tosyloxy-2,4-p en ta d ion e: mp 82 °C (lit.4b 82-83 °C); IR
(KBr) 3060, 1600, 1370, 1200, 1180, 800 cm-1 1H NMR (400
;
MHz, CDCl3) 1.96 (s, 6H), 2.49 (s, 3H), 4.49 (s, 1H), 7.40 (d, J )
7.8 Hz, 2H), 7.83 (d, J ) 8.3 Hz, 2H).
r-Tosyloxy-p-ch lor oa cetop h en on e: mp 122 °C (lit.4b 125
1
°C); IR (KBr) 1710, 1360, 1190, 810 cm-1; H NMR (400 MHz,
CDCl3) 2.46 (s, 3H), 5.21 (s, 3H), 7.35 (d, J ) 8.3 Hz, 2H), 7.45
(dt, J ) 8.9, 2.3 Hz, 2H), 7.80 (dt, J ) 9.0, 2.2 Hz, 2H), 7.84 (dt,
J ) 7.2, 2.3 Hz, 2H).
r-Tosyloxy-p-m eth yla cetop h en on e: mp 80 °C (lit.9 82-
83 °C); IR (KBr) 1700, 1350, 1170, 810 cm-1; 1HNMR (400 MHz,
CDCl3) 2.41 (s, 3H), 2.45 (s, 3H), 5.24 (s, 2H), 7.26 (d, J ) 8.0
Hz, 2H), 7.35 (d, J ) 7.9 Hz, 2H), 7.74 (d, J ) 8.2 Hz, 2H), 7.86
(d, J ) 8.4 Hz, 2H).
(Tosyloxy)m eth yl 2-th ien yl k eton e: mp 92-93 °C (lit.10
1
94-96 °C); IR (KBr) 1685, 1370, 1180, 730 cm-1; HNMR (400
MHz, CDCl3) 2.45 (s, 3H), 5.09 (s, 2H), 7.16 (dd, J ) 4.8, 3.9 Hz,
1H), 7.35 (d, J ) 8.0 Hz, 2H), 7.73 (dd, J ) 5.0, 1.1 Hz, 1H),
7.79 (dd, J ) 3.9, 1.0 Hz, 1H), 7.85 (d, J ) 8.2 Hz, 2H).
(Tosyloxy)m eth yl 2-fu r a n yl k eton e: mp 63-64 °C (lit.10
1
65-67 °C); IR (KBr) 1695, 1370, 1170, 810, 750 cm-1; H NMR
Poly{R-methyl[4-(diacetoxy)iodo]styrene} was prepared under
the same conditions as those described above: IR (KBr) 1640
(br), 1560 (br), 1480, 1400, 1050, 1000, 760 (br) cm-1. Anal.
Found: C, 43.61; H, 4.27; I, 34.21.
P r ep a r a tion of P oly[4-h yd r oxy(tosyloxy)iod o)]styr en e.
Poly[4-(diacetoxyiodo)styrene] (10 mmol) was added to the
solution of p-toluenesulfonic acid monohydrate (20 mmol) in
chloroform (20 mL) and stirred for 24 h at room temperature
under dark conditions. After the reaction was completed, diethyl
ether (50 mL) was added to the reaction mixture. The mixture
was filtered, and the solid was washed with diethyl ether: IR
(400 MHz, CDCl3) 2.45 (s, 3H), 5.09 (s, 2H), 6.58 (dd, J ) 3.7,
1.7 Hz, 1H), 7.33 (dd, J ) 3.7, 0.8 Hz, 1H), 7.36 (d, J ) 8.1 Hz,
2H), 7.61 (dd, J ) 1.7, 0.7 Hz, 1H), 7.86 (d, J ) 8.5 Hz, 2H).
4-P h en yl-2-tosyloxybu ta n a l: oil; IR (neat) 1740, 1360,
1180, 700 cm-1; 1H NMR (400 MHz, CDCl3) 1.91-1.62 (m, 2H),
2.48 (s, 3H), 2.54 (t, J ) 7.8 Hz, 2H), 4.59 (ddd, J ) 6.8, 6.0, 1.4
Hz, 1H), 7.01 (d, J ) 7.5 Hz, 2H), 7.15-7.31 (m, 3H), 7.37 (q, J
) 8.5 Hz, 1H), 7.82 (d, J ) 8.5 Hz, 2H), 9.55 (d, J ) 1.5 Hz, 1H).
(9) Khanna, M. S.; Grag, C. P.; Kapoor, R. P. Tetrahedron Lett. 1992,
33, 1495.
(8) Tuncay, A.; Dustman, J . A.; Fisher, G.; Tuncay, C. I. Tetrahedron
Lett. 1992, 33, 7647.
(10) Moriarty, R. M.; Penmasta, R.; Awasthi, A. K.; Epa, W. R.;
Prakash, I. J . Org. Chem. 1989, 54, 1101.