Photo-Fries rearrangement of N-arylsulfonamides to aminoaryl sulfone derivatives

Article abstract of DOI:10.1016/j.tet.2003.08.006

Photochemical reaction of variously substituted p-toluenesulfonanilides was studied. The reaction gives rearranged products, o- and p-amino-substituted diaryl sulfones with the combined yields of 38-72%: the p-isomer is more favored over the o-isomer with the selectivity ratio of 1.1-4.3 depending on the substituents. N-Alkylation of the sulfonanilides increases the yields of the rearranged products, and e-withdrawing substituents on the N-phenyl ring does not lower the yields drastically. This study provides simple methodology for the synthesis of o- and p-aminoaryl sulfones which are otherwise not easily accessible.

Full text of DOI:10.1016/j.tet.2003.08.006

Tetrahedron 59 (2003) 7651–7659
Photo-Fries rearrangement of N-arylsulfonamides to aminoaryl
sulfone derivatives
*
Kwanghee Koh Park, Jin Joo Lee and Jaegyung Ryu
Department of Chemistry, Chungnam National University, Yu-Sung-Ku, Taejon 305-764, South Korea
Received 23 June 2003; revised 7 August 2003; accepted 7 August 2003
Abstract—Photochemical reaction of variously substituted p-toluenesulfonanilides was studied. The reaction gives rearranged products, o-
and p-amino-substituted diaryl sulfones with the combined yields of 38–72%: the p-isomer is more favored over the o-isomer with the
selectivity ratio of 1.1–4.3 depending on the substituents. N-Alkylation of the sulfonanilides increases the yields of the rearranged products,
and e-withdrawing substituents on the N-phenyl ring does not lower the yields drastically. This study provides simple methodology for the
synthesis of o- and p-aminoaryl sulfones which are otherwise not easily accessible.
q 2003 Elsevier Ltd. All rights reserved.
1. Introduction
photolytically to o-aminophenyl sulfones. On the other
hand, Weiss and co-workers reported the formation of the
both, o- and p-rearranged products,14 while Badr et al. could
not observe the isomeric aminophenyl phenyl sulfones from
the photolysis of N-arylarenesulfonamides.16 There is also a
report that photolysis of benzenesulfonanilide gave only
4-aminodiphenyl sulfone in isotropic media, but 2-amino-
diphenyl sulfone is obtained exclusively upon cyclodextrin
encapsulation.15 On the other hand, Henning et al. reported
that N-tosyl-b-aminovinyl phenyl ketones rearrange photo-
chemically to a-tosyl-b-aminovinyl phenyl ketones.17
Aminoaryl sulfone derivatives are important class of
compounds since they show interesting biological and
pharmacological properties such as inhibitory effect on
Escherichia coli dihydropteroate synthase and anti-
inflammatory activity.1–6 The aminoaryl sulfones have
usually been prepared by reduction of the corresponding
nitroaryl sulfones.1,2 The nitroaryl sulfones are obtained
either from sulfonylation of arenes using nitroaryl sulfonyl
chloride in the presence of Lewis acid1 or from oxidation of
nitroaryl sulfides which are prepared from the reaction of
chloronitrobenzene with thiophenol derivatives.2 These
procedures have their own drawbacks: the sulfonylation
approach suffers from inefficiency with arenes bearing
strongly electron-withdrawing substituents, and the
oxidation process is limited by the availability of sulfides.
In this paper, we carried out a systematic study on the
photochemical reaction of N-arylsulfonamides using a wide
range of variously substituted N-aryl-p-toluenesulfon-
amides to find out the scope of the reaction and to exploit
the reaction as a methodology for the synthesis of
aminoarylsulfones.
The aminoaryl sulfones have also been prepared via
rearrangement of N-arylsulfonamide derivatives either
chemically7–12 or photochemically,12–15 but the studies
are rather limited. Moreover, p-aminoaryl sulfones were not
obtained by chemically induced rearrangement of the
sulfonamides.7–12 Also, the product selectivities of the
photochemical reactions of N-aryl sulfonamides are widely
different among the reports.12–16 Nozaki et al.13 reported
that irradiation of arenesulfonanilides yielded exclusively
p-amino-substituted diaryl sulfones without formation of
o-amino-substituted products, while Hellwinkel et al.12 later
described that N-p-tolyl-benzenesulfonamides rearrange
2. Results and discussion
Various N-aryl-p-toluenesulfonamides were easily prepared
in almost quantitative yields by tosylation of aniline
derivatives with tosyl chloride in the presence of pyridine
in CH2Cl2. N-Alkyl-N-aryl-p-toluenesulfonamides were
obtained in more than 90% yields by alkylation of N-aryl-
p-toluenesulfonamides with alkyl halide in the presence of
potassium carbonate in DMF solvent. Figure 1 depicts the
various p-toluenesulfonanilides prepared and used in this
study.
Keywords: photo-Fries rearrangement; arenesulfonanilides; aminoaryl
sulfones.
To check the scope and feasibility of the reaction, we
first studied the photoreaction of p-toluenesulfonamide of
*
Corresponding author. Tel.: þ82-42-821-5479; fax: þ82-42-823-1360;
e-mail: khkoh@cnu.ac.kr
0040–4020/$ - see front matter q 2003 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2003.08.006

7652
K. K. Park et al. / Tetrahedron 59 (2003) 7651–7659
Figure 1. p-Toluenesulfonanilide derivatives prepared and used in the present study.
Scheme 1. Photoreaction of p-toluenesulfonamides 1a–c of o-(N-alkylamino)benzophenones.
o-(N-alkylamino)benzophenone 1a–c considering the fol-
lowing two points. One is that it is generally known that in
the photo-Fries rearrangement of aryl esters the presence of
electron-withdrawing substituents (for instance acyl groups)
in the phenolic ring inhibits the rearrangement.18,19 The
other is that the compounds 1a–c could lead to photo-
cyclized products (vide infra).
that photodeacylation occurs from the p,pp excited state of
the acylamino ketone and dealkylation proceeds via
intramolecular d-hydrogen abstraction occurring in the
charge-transfer state from the n,pp excited state.23
Table 1 summarizes the yields and the products distribution
obtained in the photoreaction of 1a under various con-
ditions. It shows that the conversion rate of the starting
material is slowest in benzene24 and getting faster in the
order of acetonitrile, t-butanol, and then methanol solvent:
almost all the starting material disappeared in methanol,
t-butanol, and acetonitrile solvents after 4 h of irradiation
1 mM solution of 1a–c in a quartz vessel was irradiated
with 254 nm lamps for 4 h under a nitrogen atmosphere.
Separation of the reaction mixture by column chromato-
graphy gave o- and p-rearranged products, 2a–c and 3a–c,
together with the detosylated compounds 4a–c (Scheme 1).
The detosylated and dealkylated product 5 was obtained in
less than 5% yield. The compound 6 and/or 7, which would
be formed if photocyclization reaction via d-hydrogen
abstraction20–22 had occurred, were not detected.
Table 1. Yields and product distribution obtained after photoirradiation of
1 mM solution of 1a for 4 h
Solvent
l (nm) Recovered 1a (%)
Yield (%)
2a 3a 4a
5
2aþ3a
Photoirradiation of 1a–c was also carried out using 350 nm
lamps instead of 254 nm since it was reported that near UV
irradiation of o-benzoyl N-alkylanilinium ions and
b-aminovinyl phenyl ketones leads to the photocyclized
products20,21 and also the photocyclization reaction of
o-alkoxybenzophenones to benzofuran derivatives proceeds
effectively with 350 nm light.22 After 4 h, the reaction
mixture showed very low conversion of the starting material
and the cyclized products were not detected. This is
reminiscent of a report23 that o-(N-alkylacylamino)benzo-
phenones undergo primarily photolytic deacylation and
dealkylation without formation of indoles. It was suggested
Benzene
MeOH
254
350
27
86
15 19 23 nd 34(47)a
nd nd
6
2
nd
254
350
nd
66
16 18 22
3
2
2
34
8(24)a
5
5
CH3CN
t-BuOH
254
350
3
78
21 30 17 nd 51(53)a
3
2
4
nd 5(23)a
254
350
nd
72
22 26 23
5
48
7(25)a
2
9
1
The yields are isolated yields. nd: not detected.
a
The yields in parentheses are calculated on the consumed 1a.

K. K. Park et al. / Tetrahedron 59 (2003) 7651–7659
7653
Scheme 2. Photoreaction of p-toluenesulfonamides 1d–l of various aniline derivatives.
with 254 nm lamps. The combined yields of the rearranged
products, o- and p-aminosulfones based on the consumed 1a
are ca. 50% except in methanol solvent where the yield is
34%. It would be worth mentioning that though it is
generally believed that polar solvents such as methanol
favor the rearrangement in the photo-Fries rearrangement of
phenyl esters,26 Pitchumani et al.27 found little difference in
the yields of the rearranged products in methanol and
benzene. Table 1 also shows that formation of p-isomer is a
little more favored than o-isomer in all the solvents
employed here and the selectivity is greatest in acetonitrile
solvent as 1.4. The detosylated product 4a is obtained in ca.
20% yield and the detosylated and dealkylated product 5 is
produced in less than 5% yield. The photoreaction of 1a
with 350 nm lamps results in very low conversion and gave
small amounts of 2a and 3a except in benzene where the
rearranged products were not detected. Similar results
were obtained with the sulfonamides 1b and 1c: the
reactions were slowest in benzene and the combined
yields of the rearranged products and the ratios of the p-
to o-aminoarylsulfones were highest in acetonitrile
solvent.
Since we found that the photoirradiation of the sulfonamides
1a–c with highly electron-withdrawing substituents with
254 nm light gives o- and p-amino-substituted arylsulfone
derivatives with modest yields, we proceeded with the
photoreaction using variously substituted sulfonamides 1d–
l to find out the substituent effects and the scope of the
reaction. 5 mM solutions of various sulfonamides 1d–l
were irradiated with 254 nm lamps in acetonitrile solvent
and the products were separated to provide the amino-
arylsulfones 2d–l and/or 3d–l (Scheme 2). The detosylated
compounds 4d–l were obtained with less than 3% yields,
which is in contrast to ca. 20% yields of 4a–c from 1a–c.
The yields of the rearranged products, o- and p-amino-
arylsulfones are listed in Table 2, where the data obtained
from 1a–c are also included for comparison.
Table 2 shows that photoirradiation of 1d gives both
o-aminophenyl tolyl sulfone 2d and p-aminophenyl tolyl
sulfone 3d with 15 and 32% isolated yields, respectively, in
contrast to the previous reports of the formation of only the
p-isomer with 7% isolated yield (25% yield based on the
consumed starting material)13 and the formation of both
Table 2. Yields of o- and p-aminoaryl sulfones obtained from the photoirradiation of various p-toluenesulfonanilides in CH3CN using 254 nm lamps
Entry
Starting material, 1
X
Y
R0
Reaction time (h)
Yield of aminoaryl sulfones (%)
o-isomer, 2
p-isomer, 3
2þ3
51
52
38
1
2
3
4
1a
1b
1c
1d
1d
1d
1e
1f
1g
1h
1i
1i
1i
COPh
COPh
COPh
H
H
H
H
H
H
OCH3
H
H
H
Cl
H
F
H
H
H
H
H
H
H
OCH3
OCH3
H
Cl
Cl
Cl
H
F
H
CH3
Et
C8H17
H
H
H
CH3
H
CH3
H
H
H
4
4
4
4
10
21
22
14
15
nd
6
26
30
30
24
32
47
5a
6c
7
7(25)b
13
26
7(25)b
19
52
Not given
4
5
8
9
59
72
nd
nd
59
72
4
4
10
11
12
13
14
15
16
25
27
nd
12f(13)b
16f
32
52
0.5d
2e
5
20(39)b
28(30)b
25g
18(5)h
39
20(39)b
40(43)b
41
H
H
H
H
1j
1k
1l
4
4
5
55
39
47
nd
29
18
5 mM solution was irradiated except for 1a–c where 1 mM solution was used. The yields are isolated yields. nd: not detected.
From Ref. 13: solvent was n-butanol.
a
b
The yields in parentheses are calculated on the consumed starting materials.
From Ref. 14: solvent was diethyl ether and the reaction time was not mentioned.
49% of the starting material was recovered.
6% of the starting material was recovered.
c
d
e
f
Dechlorinated p-rearranged product, 3d was obtained.
1:1 mixture of 2i and 2d.
5% of the dechlorinated o-rearranged product, 2d was obtained together with 18% yield of 2j.
g
h

7654
K. K. Park et al. / Tetrahedron 59 (2003) 7651–7659
isomers with the combined yield of less than 20%.14 Table 2
also shows that both o- and p-aminoarylsulfones are formed
from all the arylsulfonamides studied here (see entries 1–4,
7, 10, 14, and 16) unless the corresponding positions are
already occupied with substituents, and the formation of the
p-isomer is always favored over the o-isomer. The para to
ortho selectivity ratio varies from 1.1 for 1h (entry 10) to 4.3
for 1d (entry 4): when two o-positions of the starting
material are unsubstituted, the selectivity ratio is twice
the ratio of the yields. Clarification of the origin for
this selectivity is beyond the scope of this work, but it
might be worth to mention that the photo-Fries rearrange-
ments of phenyl esters show no general trend of the
selectivity.15,18,27–29
Table 3. 1H chemical shifts (d) of the amine protons of o- and p-aminoaryl
sulfones in CDCl3 solvent
Entry Compound
X
Y
R0
d value of amine protons
o-isomer, 2 p-isomer, 3
1
2
3
4
5
6
7
8
a
b
c
d
e
f
g
h
i
COPh
COPh
COPh
H
H
H
H
H
H
H
H
CH3
Et
C8H17 6.37
H
CH3
H
6.65
6.30
8.94
8.93
9.02
4.17
4.38
–
–
4.30
–
5.12
6.31
4.79
5.94
5.37
5.13
5.61
4.98
5.22
OCH3
OCH3 CH3
H
Cl
H
F
H
OCH3
H
Cl
H
F
H
H
H
H
H
9
10
11
12
j
k
l
4.57
–
4.27
H
The combined yields of the rearranged products, 2 and 3
vary from ca. 40% (entries 3, 12, 13, and 15) to 72% (entry
9). Table 2 indicates that N-alkylation of sulfonanilides
increases the yields of the sulfones (see entry 4 vs 7 and
entry 8 vs 9). Introduction of electron-donating substituents
often gives higher yields of the rearrangement products
(compare entries 7 and 9, and also entries 4, 8, 10, 13, and
15), but the trend is not always hold (compare entries 1 and
7, and also entries 4 and 16).
possible in the o-isomers. However, the situation is reversed
in the aminoarylsulfones substituted with o-benzoyl group
(entries 1–3): the amine proton of 2-amino-3-benzoyl-
phenyl sulfones 2a–c appear at d 6.3–6.7, while those of
the corresponding p-amino isomers 3a–c are in the range of
d 8.9–9.0. This suggests that when the amine group is
located at ortho position both to the benzoyl group and
sulfonyl group, the amine hydrogen is hydrogen-bonded to
the sulfonyl oxygen rather than to the carbonyl oxygen
atom: the chemical shifts of the amine protons of 2a–c are
in the same range with those observed in other o-aminoaryl
sulfones (compare entries 1–3 with entries 5 and 7), while
the chemical shifts of the amine protons of 3a–c are in the
similar range with other o-aminobenzophenone compounds
such as 4a–c whose chemical shifts are d 8.5–8.6 (Section
4).
Table 2 also shows that dechlorinated products are formed
in the photoreaction of 1i and 1j: only 2-amino-5-
chlorophenyl p-tolyl sulfone 2i was detected from
irradiation of N-p-chlorophenylsulfonamide 1i for 0.5 h
(entry 11), but dechlorinated products, o- and p-aminophe-
nylsulfones, 2d and 3d are formed after longer irradiation
(entries 12 and 13). N-o-Chlorophenylsulfonamide 1j also
gives small amount of dechlorinated product, o-amino-
phenylsulfone 2d in addition to the simply rearranged
products 2j and 3j. Similar to this, dechlorinated products
have been reported in the photo-Fries reaction of phenyl
benzoates.18,30 The dechlorinated products 2d and 3d could
be formed either via the diene intermediates 8j and 8i,
respectively, or via initial dechlorination from the starting
N-chlorophenylsulfonamides 1i–j followed by rearrange-
ment of the sulfonyl group: irradiation of the rearranged
sulfones 2i and 2j under the same conditions for the
photochemical reaction of 1i and 1j gave no appreciable
amounts of the dechlorinated products (Scheme 3).
The fact that the amine hydrogen is not hydrogen-bonded to
CO in the compounds 2a–c is also manifested in their IR
spectra: the carbonyl absorption bands of 2a–c (1646–
1661 cm21) appear at 21–34 cm21 higher wavenumbers
than the corresponding 3a–c (1622–1627 cm21) where
internal hydrogen bonding between the amine hydrogen and
carbonyl group shifts the carbonyl absorption to lower
wavenumbers.
Energy calculation provided further support for the presence
of the hydrogen bonding between NH and SO rather than
between NH and CO. The energy-minimized structures of
2a by MM2 modelling suggested that two conformations
with different distances between the amine hydrogen and the
oxygen atoms are energetically feasible. In one form, the
distance between the amine hydrogen and the sulfonyl
Finally, we would like to mention that the structures of
ortho- and para-aminophenyl sulfones are clearly differ-
entiated by their NMR data, especially the chemical shifts of
amino protons, which are listed in Table 3. The table shows
that the amine proton(s) of o-aminophenylsulfone deriva-
tives absorb at lower field (Dd is ca. 1 ppm) than the amine
proton(s) of the corresponding p-isomers (entries 4, 5, 8, 10,
and 12), which is well expected since the hydrogen bonding
between the amine hydrogen and sulfonyl oxygen atom is
˚
oxygen atom is 1.79 A, while the distance between the
˚
hydrogen and the carbonyl oxygen atom is 4.68 A. In the
˚
other form, the corresponding distances are 4.42 and 1.84 A,
respectively. The former appeared to be more stable than the
latter by 3.5 kcal/mol. This is consistent with NMR and IR
results.
3. Conclusions
We have shown that photochemical reaction of variously
substituted p-toluenesulfonanilides provides moderate
yields of o- and p-aminophenyl sulfone derivatives with
Scheme 3.

K. K. Park et al. / Tetrahedron 59 (2003) 7651–7659
7655
the para to ortho selectivity ratio of 1.1–4.3 depending on
the substituents. N-Alkylation of the sulfonanilides
increases the yields of the rearranged products, and
electron-withdrawing substituents on the N-phenyl ring
does not lower the yields drastically. The results presented
here would provide a simple route for the synthesis of o- and
p-aminoarylsulfones which are not easily accessible by
other methods.
7.14 (d, 1H, J¼8 Hz), 7.09 (d, 2H, J¼8 Hz), 3.67 (q, 2H,
J¼7 Hz), 2.31 (s, 3H), 1.16 (t, 3H, J¼7 Hz). IR (KBr):
1660, 1595, 1328, 1168, 1146, 711 cm21. UV (CH3CN):
lmax (1) 242 nm (23000). Anal. calcd for C22H21NO3S: C,
69.63; H, 5.58; N, 3.69; S, 8.45. Found: C, 70.01; H, 5.62;
N, 3.43; S, 8.12.
4.2.3. Compound 1c. Rf 0.58 (hexane–ethyl acetate, 4:1);
oil; 1H NMR (CDCl3, 400 MHz) d 7.78–7.75 (m, 2H), 7.56
(t, 1H, J¼7 Hz), 7.48–7.35 (m, 7H), 7.16 (d, 1H, J¼8 Hz),
7.08 (d, 2H, J¼8 Hz), 3.56 (t, 2H, J¼8 Hz), 2.31 (s, 3H),
1.56 (br s, 2H), 1.30–1.16 (m, 10H), 0.86 (t, 3H, J¼7 Hz).
IR (KBr): 1668, 1597, 1346, 1159, 753 cm21. UV
(CH3CN): lmax (1) 241 nm (24000). Anal. calcd for
C28H33NO3S: C, 72.54; H, 7.17; N, 3.02; S, 6.92. Found:
C, 72.87; H, 7.28; N, 3.07; S, 6.68.
4. Experimental
4.1. General
1H NMR and 13C NMR spectra were obtained using
tetramethylsilane as an internal standard. The molecular
modelling calculations were carried out with MM2 force
field provided by Cambridgesoft. Melting points are
uncorrected.
4.2.4. Compound 1d. Rf 0.59 (hexane–ethyl acetate, 2:1);
mp 104–1058C (lit.31 103–1048C); 1H NMR (CDCl3,
500 MHz) d 7.69 (d, 2H, J¼8 Hz), 7.25 (br s, 1H, –NH),
7.23–7.20 (m, 4H), 7.10–7.06 (m, 3H), 2.36 (s, 3H). UV
(CH3CN): lmax (1) 221 nm (16000).
4.2. General procedure for the synthesis of N-aryl-p-
toluenesulfonamides 1a–l
4.2.5. Compound 1e. Rf 0.70 (hexane–ethyl acetate, 2:1);
mp 95–978C (lit.32 93–958C); 1H NMR (CDCl3, 500 MHz)
d 7.42 (d, 2H, J¼8 Hz), 7.32–7.22 (m, 5H), 7.11–7.07 (m,
2H), 3.16 (s, 3H), 2.42 (s, 3H). UV (CH3CN): lmax (1)
227 nm (11000).
To a mixture of aniline derivative (30 mmol) and pyridine
(15 ml, 180 mmol) in dichloromethane (100 ml) was added
slowly p-toluenesulfonyl chloride (6.86 g, 36 mmol). The
reaction mixture was stirred at room temperature for 16 h
for o-aminobenzophenone or 0.5 h for other aniline
derivatives. The reaction mixture was concentrated to ca.
50 ml, and then washed with 5% HCl. The organic layer was
dried over sodium sulfate, filtered, and evaporated to afford
a residue. Purification of the residue by silica gel column
chromatography provided the corresponding N-aryl-p-
toluenesulfonamide 1d, 1f, or 1h–l in 90–100% yields.
4.2.6. Compound 1f. Rf 0.51 (hexane–ethyl acetate, 2:1);
mp 114.7–115.58C (lit.33 114.5–1158C); 1H NMR (CDCl3,
300 MHz) d 7.60 (d, 2H, J¼8 Hz), 7.20 (d, 2H, J¼8 Hz),
6.99 (d, 2H, J¼9 Hz), 6.80 (s, 1H, –NH), 6.75 (d, 2H,
J¼9 Hz), 3.74 (s, 3H), 2.37 (s, 3H). UV (CH3CN): lmax (1)
225 nm (18000).
For preparation of N-alkyl-N-aryl-p-toluenesulfonamides
1a–c, 1e, and 1g, appropriate alkyl halide (7.5–10 mmol)
was added slowly to a reaction mixture of N-aryl-p-
toluenesulfonamide (5 mmol) and potassium carbonate
(4.15 g, 30 mmol) in 20 ml of DMF and stirred: reaction
temp and reaction time are room temperature and 1 h for the
reaction with methyl iodide, room temperature and 15 h for
ethyl iodide, and 708C and 20 h for octyl bromide. After
concentrating the reaction mixture, dichloromethane
(20 ml) was added to the residue and washed with distilled
water. The organic layer was dried over sodium sulfate,
filtered, and evaporated to afford a residue. Purification of
the residue by silica gel column chromatography provided
the corresponding N-alkyl-N-aryl-p-toluenesulfonamide in
more than 90% yield.
4.2.7. Compound 1g. Rf 0.67 (hexane–ethyl acetate, 2:1);
mp 62–648C (lit.11 61–628C); 1H NMR (CDCl3, 300 MHz)
d 7.44 (d, 2H, J¼8 Hz), 7.24 (d, 2H, J¼8 Hz), 7.01–6.95
(m, 2H), 6.83–6.78 (m, 2H), 3.79 (s, 3H), 3.13 (s, 3H), 2.42
(s, 3H). UV (CH3CN): lmax (1) 227 nm (18000).
4.2.8. Compound 1h. Rf 0.48 (hexane–ethyl acetate, 2:1);
mp 130.4–131.68C (lit.34 146–1478C; lit.35 128.5–
129.58C); 1H NMR (CDCl3, 300 MHz) d 7.64 (d, 2H,
J¼8 Hz), 7.51 (d, 1H, J¼8 Hz), 7.18 (d, 2H, J¼8 Hz), 7.02
(t, 1H, J¼8 Hz), 7.00 (s, 1H, –NH), 6.88 (t, 1H, J¼8 Hz),
6.73 (d, 1H, J¼8 Hz), 3.63 (s, 3H), 2.35 (s, 3H). IR (KBr):
3333, 1595, 1500, 1335, 1159, 754, 661 cm21. Anal. calcd
for C14H15NO3S: C, 60.63; H, 5.45; N, 5.05; S, 11.56.
Found: C, 60.41; H, 5.45; N, 4.75; S, 11.52. UV (CH3CN):
l
max (1) 221 nm (16000), 277 nm (3300).
4.2.1. Compound 1a. Rf 0.25 (hexane–ethyl acetate, 5:1);
mp 131–1328C; 1H NMR (CDCl3, 300 MHz) d 7.79 (d, 2H,
J¼8 Hz), 7.57 (t, 1H, J¼8 Hz), 7.49–7.39 (m, 7H), 7.15 (d,
2H, J¼8 Hz), 6.97 (d, 1H, J¼8 Hz), 3.09 (s, 3H), 2.37 (s,
4.2.9. Compound 1i. Rf 0.58 (hexane–ethyl acetate, 2:1);
mp 97.4–98.88C (lit.33 94–958C); 1H NMR (CDCl3,
300 MHz) d 7.67 (d, 2H, J¼8 Hz), 7.32 (s, 1H, –NH),
7.23 (d, 2H, J¼8 Hz), 7.21–7.15 (m, 2H), 7.06–7.00 (m,
2H), 2.38 (s, 3H). UV (CH3CN): lmax (1) 227 nm (18000).
3H). IR (KBr): 1670, 1593, 1446, 1342, 1159, 709 cm21
.
UV (CH3CN): lmax (1) 238 nm (22000). Anal. calcd for
C21H19NO3S: C, 69.02; H, 5.24; N, 3.83; S, 8.77. Found: C,
69.30; H, 5.23; N, 3.61; S, 8.81.
4.2.10. Compound 1j. Rf 0.41 (hexane–ethyl acetate, 5:1);
mp 109.5–110.28C (lit.36 1028C); 1H NMR (CDCl3,
300 MHz) d 7.65 (d, 3H, J¼8 Hz), 7.26–7.19 (m, 4H),
7.02 (t, 1H, J¼8 Hz), 6.98 (s, 1H, –NH), 2.37 (s, 3H). IR
4.2.2. Compound 1b. Rf 0.45 (dichloromethane–hexane,
1
5:1); mp 129–1318C; H NMR (CDCl3, 400 MHz) d 7.77
(d, 2H, J¼8 Hz), 7.56 (t, 1H, J¼7 Hz),7.48–7.37 (m, 7H),

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K. K. Park et al. / Tetrahedron 59 (2003) 7651–7659
(KBr): 3263, 1593, 1482, 1397, 1334, 1167, 903, 750 cm21
UV (CH3CN): lmax (1) 221 nm (sh, 15000). Anal. calcd for
C13H12NO2ClS: C, 55.42; H, 4.29; N, 4.97; S, 11.38. Found:
C, 55.31; H, 4.46; N, 4.79; S, 11.20.
.
5H), 6.75 (d, 1H, J¼8 Hz), 6.53 (t, 1H, J¼8 Hz), 2.96 (d,
3H, J¼5 Hz).
4.3.4. Compound 2b. Rf 0.29 (hexane–ethyl acetate, 5:1);
1
mp 162–1648C; H NMR (CDCl3, 400 MHz) d 8.10 (dd,
4.2.11. Compound 1k. Rf 0.58 (hexane–ethyl acetate,
2:1); mp 80–828C (lit.37 808C); 1H NMR (CDCl3,
400 MHz) d 7.63 (d, 2H, J¼8 Hz), 7.22 (d, 2H, J¼8 Hz),
7.11 (br s, 1H, –NH), 7.05 (dd, 2H, J¼9, 5 Hz), 6.91 (t, 2H,
J¼8 Hz), 2.38 (s, 3H). UV (CH3CN): lmax (1) 221 nm
(14000).
1H, J¼8, 2 Hz), 7.80 (dd, 2H, J¼8, 2 Hz), 7.77 (d, 2H,
J¼8 Hz), 7.58 (t, 1H, J¼7 Hz), 7.44 (t, 2H, J¼7 Hz), 7.37
(dd, 1H, J¼8, 1 Hz), 7.30 (d, 2H, J¼8 Hz), 6.80 (t, 1H,
J¼8 Hz), 6.30 (br s, 1H, –NH), 2.70–2.65 (m, 2H), 2.42 (s,
3H), 0.98 (t, 3H, J¼7 Hz); 13C NMR (CDCl3, 100 MHz) d
15.48, 21.55, 42.89, 115.59, 124.81, 126.37, 127.08, 128.54,
129.72, 130.09, 132.84, 133.35, 136.75, 136.98, 138.41,
144.27, 146.46, 196.02. IR (KBr): 3390, 1646, 1588, 1459,
1322, 1255, 1146, 954 cm21. Anal. calcd for C22H21NO3S:
C, 69.63; H, 5.58; N, 3.69; S, 8.45. Found: C, 69.93; H, 5.52;
N, 3.42; S, 8.15.
4.2.12. Compound 1l. Rf 0.51 (hexane–ethyl acetate, 2:1);
1
mp 107.8–110.48C (lit.38 108–1098C); H NMR (CDCl3,
400 MHz) d 7.66 (d, 2H, J¼8 Hz), 7.58 (dt, 1H, J¼8, 2 Hz),
7.21 (d, 2H, J¼8 Hz), 7.10–7.02 (m, 2H), 6.97–6.91 (m,
1H), 6.80 (br s, 1H, –NH), 2.37 (s, 3H). UV (CH3CN): lmax
(1) 221 nm (15000).
4.3.5. Compound 3b. Rf 0.15 (hexane–ethyl acetate, 5:1);
1
mp 121–1238C; H NMR (CDCl3, 400 MHz) d 8.93 (br s,
4.3. Photoreaction of N-aryl-p-toluenesulfonamides 1a–l
1H, –NH), 8.09 (d, 1H, J¼2 Hz), 7.82 (dd, 1H, J¼9, 2 Hz),
7.71 (d, 2H, J¼8 Hz), 7.58–7.54 (m, 3H), 7.47 (t, 2H,
J¼8 Hz), 7.26 (d, 2H, J¼8 Hz), 6.78 (d, 1H, J¼9 Hz),
3.36–3.27 (m, 2H), 2.38 (s, 3H), 1.34 (t, 3H, J¼7 Hz); 13C
NMR (CDCl3, 100 MHz) d 14.12, 21.46, 37.51, 111.90,
116.05, 125.65, 127.02, 128.36, 129.23, 129.73, 131.78,
133.07, 135.90, 139.09, 139.84, 143.43, 153.92, 198.38. IR
(KBr): 3297, 1622, 1316, 1257, 1140, 1092 cm21. Anal.
calcd for C22H21NO3S: C, 69.63; H, 5.58; N, 3.69; S, 8.45.
Found: C, 69.60; H, 5.64; N, 3.57; S, 8.38.
1 or 5 mM solution (700 ml) of 1a–l contained in a quartz
vessel was purged with nitrogen for 1 h and then irradiated
under nitrogen with 254 nm mercury lamp using RPR-100
photochemical reactor (Southern New England Ultraviolet
Company) for desired period. The solvent was removed
under reduced pressure and the residue was separated by
silica gel column chromatography. Irradiation experiments
with 350 nm lamps were carried out similarly for com-
pounds 1a–c. The yields of the products are listed in
Tables 1 and 2, and characterization data of the products are
given below.
4.3.6. Compound 4b. Rf 0.66 (hexane–ethyl acetate, 5:1);
oil (lit.40 34.5–35.58C); 1H NMR (CDCl3, 300 MHz) d 8.51
(br s, 1H, –NH), 7.59 (d, 2H, J¼8 Hz), 7.50–7.34 (m, 5H),
6.76 (d, 1H, J¼9 Hz), 6.51 (t, 1H, J¼8 Hz), 3.35–3.25 (m,
2H), 1.35 (t, 3H, J¼7 Hz). IR (KBr): 3326, 1618, 1572,
1518, 1257, 1216, 1165, 758 cm21. Anal. calcd for
C15H15NO: C, 79.97; H, 6.71; N, 6.22. Found: C, 79.91;
H, 6.80; N, 6.29.
4.3.1. Compound 2a. Rf 0.28 (hexane–ethyl acetate, 5:1);
1
mp 141–1438C; H NMR (CDCl3, 400 MHz) d 8.06 (dd,
1H, J¼8, 1 Hz), 7.82 (dd, 2H, J¼8, 1 Hz), 7.77 (d, 2H,
J¼9 Hz), 7.58 (t, 1H, J¼8 Hz), 7.44 (t, 2H, J¼8 Hz), 7.37
(dd, 1H, J¼8, 2 Hz), 7.30 (d, 2H, J¼8 Hz), 6.79 (t, 1H,
J¼8 Hz), 6.65 (q, 1H, J¼5 Hz, –NH), 2.54 (d, 3H, J¼5 Hz,
–NCH3), 2.41 (s, 3H); 13C NMR (CDCl3, 100 MHz) d
21.54, 34.71, 115.45, 124.79, 125.92, 126.91, 128.54,
129.80, 130.11, 132.73, 133.35, 136.75, 137.19, 138.52,
144.30, 147.69, 195.93. IR (KBr): 3391, 1648, 1587, 1517,
1398, 1321, 1246, 1144 cm21. Anal. calcd for C21H19NO3S:
C, 69.02; H, 5.24; N, 3.83; S, 8.77. Found: C, 68.93; H, 5.14;
N, 3.52; S, 8.46.
4.3.7. Compound 2c. Rf 0.28 (hexane–ethyl acetate, 9:1);
oil; 1H NMR (CDCl3, 400 MHz) d 8.09 (dd, 1H, J¼8, 2 Hz),
7.81–7.73 (m, 4H), 7.57 (t, 1H, J¼7 Hz), 7.43 (t, 2H,
J¼7 Hz), 7.38 (dd, 1H, J¼8, 2 Hz), 7.29 (d, 2H, J¼9 Hz),
6.80 (t, 1H, J¼8 Hz), 6.37 (t, 1H, J¼5 Hz, –NH), 2.65–
2.59 (m, 2H), 2.42 (s, 3H), 1.34–1.06 (m, 12H), 0.86 (t, 3H,
J¼7 Hz); 13C NMR (CDCl3, 100 MHz) d 14.04, 21.54,
22.56, 26.54, 28.99, 29.03, 30.24, 31.68, 48.23, 115.44,
124.52, 126.34, 127.00, 128.53, 129.72, 130.05, 132.91,
133.30, 136.79, 137.02, 138.53, 144.21, 146.74, 196.04. IR
4.3.2. Compound 3a. Rf 0.13 (hexane–ethyl acetate, 5:1);
1
mp 180–1828C; H NMR (CDCl3, 400 MHz) d 8.94 (br s,
1H, –NH), 8.09 (d, 1H, J¼2 Hz), 7.85 (dd, 1H, J¼9, 2 Hz),
7.71 (d, 2H, J¼8 Hz), 7.60–7.53 (m, 3H), 7.47 (t, 2H,
J¼8 Hz), 7.26 (d, 2H, J¼8 Hz), 6.77 (d, 1H, J¼9 Hz), 2.98
(d, 3H, J¼5 Hz, –NCH3), 2.38 (s, 3H); 13C NMR (CDCl3,
100 MHz) d 21.46, 29.53, 111.57, 116.30, 125.83, 127.02,
128.36, 129.21, 129.74, 131.77, 133.13, 135.76, 139.04,
139.82, 143.45, 154.86, 198.38. IR (KBr): 3308, 1627,
1599, 1303, 1263, 1165, 1098 cm21. Anal. calcd for
C21H19NO3S: C, 69.02; H, 5.24; N, 3.83; S, 8.77. Found:
C, 69.18; H, 5.53; N, 3.45; S, 8.76.
(KBr): 3373, 1661, 1592, 1456, 1318, 1249, 1150 cm21
.
Anal. calcd for C28H33NO3S: C, 72.54; H, 7.17; N, 3.02; S,
6.92. Found: C, 72.35; H, 7.24; N, 2.86; S, 6.85.
4.3.8. Compound 3c. Rf 0.21 (hexane–ethyl acetate, 9:1);
1
oil; H NMR (CDCl3, 400 MHz) d 9.02 (t, 1H, J¼5 Hz,
–NH), 8.09 (d, 1H, J¼2 Hz), 7.82 (dd, 1H, J¼9, 2 Hz), 7.71
(d, 2H, J¼8 Hz), 7.60–7.54 (m, 3H), 7.47 (t, 2H, J¼7 Hz),
7.26 (d, 2H, J¼8 Hz), 6.78 (d, 1H, J¼9 Hz), 3.28–3.23 (m,
2H), 2.39 (s, 3H), 1.70 (quintet, 2H, J¼7 Hz), 1.43 (quintet,
2H, J¼7 Hz), 1.38–1.22 (m, 8H), 0.87 (t, 3H, J¼7 Hz); 13C
NMR (CDCl3, 100 MHz) d 14.04, 21.47, 22.58, 27.03,
28.76, 29.10, 29.21, 31.74, 42.90, 111.96, 116.01, 125.54,
127.03, 128.37, 129.23, 129.74, 131.77, 133.06, 135.98,
4.3.3. Compound 4a. Rf 0.65 (hexane–ethyl acetate, 5:1);
mp 65–678C (lit.39 66–678C); 1H NMR (CDCl3, 400 MHz)
d 8.54 (br s, 1H, –NH), 7.60–7.57 (m, 2H), 7.52–7.37 (m,

K. K. Park et al. / Tetrahedron 59 (2003) 7651–7659
7657
139.12, 139.89, 143.42, 154.13, 198.42. IR (KBr): 3304,
1627, 1599, 1568, 1319, 1259, 1157, 1102 cm21. Anal.
calcd for C28H33NO3S: C, 72.54; H, 7.17; N, 3.02; S, 6.92.
Found: C, 72.52; H, 7.08; N, 2.70; S, 6.63.
N, 5.05; S, 11.56. Found: C, 60.75; H, 5.48; N, 4.75; S,
11.47.
4.3.15. Compound 2g. Rf 0.63 (hexane–ethyl acetate, 2:1);
1
mp 153.5–154.88C (lit.11 150–1518C); H NMR (CDCl3,
4.3.9. Compound 4c. Rf 0.70 (hexane–ethyl acetate, 9:1);
1
oil; H NMR (CDCl3, 400 MHz) d 8.62 (br s, 1H, –NH),
300 MHz) d 7.78 (d, 2H, J¼8 Hz), 7.43 (d, 1H, J¼3 Hz),
7.25 (d, 2H, J¼8 Hz), 7.03 (dd, 1H, J¼9, 3 Hz), 6.60 (d, 1H,
J¼9 Hz), 5.94 (br s, 1H, –NH), 3.77 (s, 3H), 2.79 (d, 3H,
J¼5 Hz), 2.38 (s, 3H); 13C NMR (CDCl3, 100 MHz) d
21.55, 30.49, 56.06, 113.21, 113.43, 121.45, 123.00, 126.71,
129.45, 138.53, 142.51, 143.76, 150.17.
7.61–7.58 (m, 2H), 7.51–7.34 (m, 5H), 6.76 (d, 1H,
J¼8 Hz), 6.50 (t, 1H, J¼8 Hz), 3.27–3.22 (m, 2H), 1.72
(quintet, 2H, J¼7 Hz), 1.46 (quintet, 2H, J¼7 Hz), 1.40–
1.22 (m, 8H), 0.88 (t, 3H, J¼7 Hz). IR (KBr): 3321, 1621,
1576, 1518, 1258, 1216, 754 cm21. Anal. calcd for
C21H27NO: C, 81.51; H, 8.79; N, 4.53. Found: C, 81.85;
H, 8.93; N, 4.34.
4.3.16. Compound 2h. Rf 0.48 (hexane–ethyl acetate, 2:1);
1
mp 98–998C; H NMR (CDCl3, 400 MHz) d 7.81 (d, 2H,
J¼8 Hz), 7.42 (d, 1H, J¼8 Hz), 7.24 (d, 2H, J¼8 Hz), 6.83
(d, 1H, J¼8 Hz), 6.91 (t, 1H, J¼8 Hz), 5.37 (br s, 2H,
–NH2), 3.81 (s, 3H), 2.36 (s, 3H); 13C NMR (CDCl3,
100 MHz) d 21.54, 55.89, 113.62, 116.19, 120.70, 121.51,
126.76, 129.46, 137.08, 138.86, 143.71, 147.29. IR (KBr):
3488, 3384, 1487, 1301, 1217, 1141 cm21. Anal. calcd for
C14H15NO3S: C, 60.63; H, 5.45; N, 5.05; S, 11.56. Found:
C, 60.48; H, 5.54; N, 4.82; S, 11.67.
4.3.10. Compound 2d. Rf 0.46 (hexane–ethyl acetate, 2:1);
mp 119.2–119.98C (lit.41 1198C); 1H NMR (CDCl3,
400 MHz) d 7.84–7.78 (m, 3H), 7.28–7.23 (m, 3H), 6.77
(t, 1H, J¼8 Hz), 6.63 (d, 1H, J¼8 Hz), 5.12 (br s, 2H,
–NH2), 2.37 (s, 3H)); 13C NMR (CDCl3, 100 MHz) d 21.56,
117.54, 117.63, 122.14, 126.81, 129.51, 129.62, 134.68,
138.67, 143.82, 145.93.
4.3.11. Compound 3d. Rf 0.15 (hexane–ethyl acetate, 2:1);
1
4.3.17. Compound 3h. Rf 0.23 (hexane–ethyl acetate, 2:1);
mp 158–1598C; 1H NMR (CDCl3, 400 MHz) d 7.76 (d, 2H,
J¼8 Hz), 7.36 (d, 1H, J¼8 Hz), 7.25 (s, 1H), 7.24 (d, 2H,
J¼8 Hz), 6.66 (d, 1H, J¼8 Hz), 4.30 (br s, 2H, –NH2), 3.85
(s, 3H), 2.36 (s, 3H); 13C NMR (CDCl3, 100 MHz) d 21.47,
55.74, 108.85, 113.12, 122.16, 126.89, 129.13, 129.55,
139.99, 141.19, 143.10, 146.11. IR (KBr): 3498, 3387,
1609, 1511, 1300, 1239, 1145, 1101 cm21. Anal. calcd for
C14H15NO3S: C, 60.63; H, 5.45; N, 5.05; S, 11.56. Found:
C, 60.73; H, 5.55; N, 4.82; S, 11.33.
mp 188.8–189.28C (lit.42 189–1938C); H NMR (CDCl3,
400 MHz) d 7.76 (d, 2H, J¼8 Hz), 7.70–7.66 (m, 2H),
7.25 (d, 2H, J¼8 Hz), 6.66–6.61 (m, 2H), 4.17 (s, 2H,
–NH2), 2.37 (s, 3H); 13C NMR (CDCl3, 100 MHz) d 21.55,
114.07, 127.02, 129.58, 129.61, 129.74, 139.89, 143.19,
150.76.
4.3.12. Compound 2e. Rf 0.68 (hexane–ethyl acetate, 2:1);
mp 142.4–144.38C (lit.12 1378C); 1H NMR (CDCl3,
400 MHz) d 7.84 (dd, 1H, J¼8, 2 Hz), 7.76 (d, 2H,
J¼8 Hz), 7.36 (t, 1H, J¼8 Hz), 7.24 (d, 2H, J¼8 Hz),
6.71 (t, 1H, J¼8 Hz), 6.62 (d, 1H, J¼8 Hz), 6.31 (br s, 1H,
–NH), 2.82 (d, 3H, J¼5 Hz), 2.37 (s, 3H); 13C NMR
(CDCl3, 100 MHz) d 21.56, 30.07, 111.61, 115.72, 121.37,
126.67, 129.48, 130.10, 135.08, 138.85, 143.67, 147.63. IR
(KBr): 3408, 1605, 1565, 1518, 1468, 1331, 1288,
1143 cm21. Anal. calcd for C14H15NO2S: C, 64.34; H,
5.79; N, 5.36; S, 12.27. Found: C, 63.54; H, 5.72; N, 5.05; S,
12.19.
4.3.18. Compound 2i. Rf 0.46 (hexane–ethyl acetate, 2:1);
mp 153–1558C; 1H NMR (CDCl3, 400 MHz) d 7.80 (d, 2H,
J¼8 Hz), 7.79 (s, 1H), 7.28 (d, 2H, J¼8 Hz), 7.19 (dd, 1H,
J¼8, 2 Hz), 6.58 (d, 1H, J¼8 Hz), 5.13 (br s, 2H, –NH2),
2.39 (s, 3H); 13C NMR (CDCl3, 100 MHz) d 21.63, 118.98,
122.32, 123.26, 126.96, 128.81, 129.69, 134.66, 138.05,
144.37, 144.46. IR (KBr): 3467, 3370, 1631, 1485, 1311,
1283, 1142 cm21. Anal. calcd for C13H12NO2ClS: C, 55.42;
H, 4.29; N, 4.97; S, 11.38. Found: C, 55.34; H, 4.35; N,
4.72; S, 11.33.
4.3.13. Compound 3e. Rf 0.29 (hexane–ethyl acetate, 2:1);
mp 147–1498C; 1H NMR (CDCl3, 500 MHz) d 7.74 (d, 2H,
J¼8 Hz), 7.66 (d, 2H, J¼8 Hz), 7.21 (d, 2H, J¼8 Hz), 6.51
(d, 2H, J¼8 Hz), 4.38 (br s, 1H, –NH), 2.80 (s, 3H), 2.33 (s,
3H); 13C NMR (CDCl3, 125 MHz) d 21.40, 29.92, 111.41,
126.91, 127.81, 129.46, 129.59, 140.27, 143.04, 152.77. IR
4.3.19. Compound 2j. Rf 0.64 (hexane–ethyl acetate, 2:1);
mp 114.8–116.98C (lit.43 1148C); 1H NMR (CDCl3,
400 MHz) d 7.80 (d, 2H, J¼8 Hz), 7.78 (dd, 1H, J¼8,
1 Hz), 7.39 (dd, 1H, J¼8, 1 Hz), 7.27 (d, 2H, J¼8 Hz), 6.71
(t, 1H, J¼8 Hz), 5.61 (br, s, 2H, –NH2), 2.39 (s, 3H); 13C
NMR (CDCl3, 100 MHz) d 21.60, 117.11, 121.05, 123.54,
126.95, 128.46, 129.65, 134.33, 138.11, 142.33, 144.26.
(KBr): 3400, 1601, 1522, 1350, 1286, 1145, 1106 cm21
.
Anal. calcd for C14H15NO2S: C, 64.34; H, 5.79; N, 5.36; S,
12.27. Found: C, 64.02; H, 5.82; N, 5.07; S, 12.02.
4.3.20. Compound 3j. Rf 0.28 (hexane–ethyl acetate, 2:1);
mp 167–1688C; 1H NMR (CDCl3, 300 MHz) d 7.80 (d, 1H,
J¼2 Hz), 7.77 (d, 2H, J¼8 Hz), 7.59 (dd, 1H, J¼9, 2 Hz),
7.27 (d, 2H, J¼8 Hz), 6.75 (d, 1H, J¼9 Hz), 4.57 (br, s, 2H,
–NH2), 2.39 (s, 3H); 13C NMR (CDCl3, 100 MHz) d 21.54,
114.74, 118.36, 127.11, 127.50, 129.08, 129.74, 130.38,
139.28, 143.64, 147.15. IR (KBr): 3461, 3363, 1636, 1588,
1499, 1335, 1297, 1147, 1117 cm21. Anal. calcd for
C13H12NO2ClS: C, 55.42; H, 4.29; N, 4.97; S, 11.38.
Found: C, 55.27; H, 4.35; N, 4.69; S, 11.46.
4.3.14. Compound 2f. Rf 0.55 (hexane–ethyl acetate, 2:1);
mp 155.1–156.38C (lit.8 147.5–148.58C); 1H NMR (CDCl3,
200 MHz) d 7.82 (d, 2H, J¼8 Hz), 7.36 (d, 1H, J¼3 Hz),
7.28 (d, 2H, J¼8 Hz), 6.92 (dd, 1H, J¼9, 3 Hz), 6.60 (d, 1H,
J¼9 Hz), 4.79 (br s, 2H, –NH2), 3.77 (s, 3H), 2.39 (s, 3H);
13C NMR (CDCl3, 100 MHz) d 21.60, 55.96, 112.03,
119.28, 122.36, 123.19, 126.88, 129.52, 138.41, 140.10,
143.92, 151.56. IR (KBr): 3426, 3347, 1497, 1304, 1284,
1142 cm21. Anal. calcd for C14H15NO3S: C, 60.63; H, 5.45;

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K. K. Park et al. / Tetrahedron 59 (2003) 7651–7659
9. Hellwinkel, D.; Supp, M. Angew. Chem. Int. Ed. Engl. 1974,
13, 270–270.
4.3.21. Compound 2k. Rf 0.45 (hexane–ethyl acetate, 2:1);
mp 143–1458C; 1H NMR (CDCl3, 400 MHz) d 7.81 (d, 2H,
J¼8 Hz), 7.54 (dd, 1H, J¼8, 3 Hz), 7.28 (d, 2H, J¼8 Hz),
7.01 (dt, 1H, J¼8, 3 Hz), 6.60 (dd, 1H, J¼9, 4 Hz), 4.98 (br
s, 2H, –NH2), 2.39 (s, 3H); 13C NMR (CDCl3, 100 MHz) d
21.61, 115.29 (d, J¼25 Hz), 118.95 (d, J¼7 Hz), 122.41 (d,
J¼22 Hz), 122.63 (d, J¼6 Hz), 127.00, 129.65, 137.97,
142.39, 144.32, 154.48 (d, J¼238 Hz). IR (KBr): 3467,
3365, 1629, 1495, 1305, 1286, 1141 cm21. Anal. calcd for
C13H12FNO2S: C, 58.85; H, 4.56; N, 5.28; S, 12.09. Found:
C, 59.04; H, 4.54; N, 5.10; S, 12.27.
10. Hellwinkel, D.; Supp, M. Chem. Ber. 1976, 109, 3749–3766.
11. Shafer, S. J.; Closson, W. D. J. Org. Chem. 1975, 40,
889–892.
12. Hellwinkel, D.; Lenz, R. Chem. Ber. 1985, 118, 66–85.
13. Nozaki, H.; Okada, T.; Noyori, R.; Kawanisi, M. Tetrahedron
1966, 22, 2177–2180.
14. Weiss, B.; Durr, H.; Haas, H. J. Angew. Chem. Int. Ed. Engl.
1980, 19, 648–650.
15. Pitchumani, K.; Manickam, M. C. D.; Srinivasan, C.
Tetrahedron Lett. 1991, 32, 2975–2978.
16. Badr, M. Z. A.; Aly, M. M.; Fahmy, A. M. J. Org. Chem. 1981,
46, 4784–4787.
4.3.22. Compound 2l. Rf 0.64 (hexane–ethyl acetate, 2:1);
mp 113–1158C; 1H NMR (CDCl3, 400 MHz) d 7.82 (d, 2H,
J¼8 Hz), 7.60 (d, 1H, J¼8 Hz), 7.28 (d, 2H, J¼8 Hz), 7.10
(t, 1H, J¼9 Hz), 6.69 (dt, 1H, J¼8, 5 Hz), 5.22 (br, s, 2H,
–NH2), 2.39 (s, 3H); 13C NMR (CDCl3, 100 MHz) d 21.61,
116.40 (d, J¼7 Hz), 119.33 (d, J¼19 Hz), 124.16 (d,
J¼2 Hz), 124.81 (d, J¼3 Hz), 126.91, 129.67, 135.46 (d,
J¼15 Hz), 138.33, 144.24, 151.40 (d, J¼241 Hz). IR (KBr):
3464, 3372, 1630, 1488, 1300, 1210, 1142 cm21. Anal.
calcd for C13H12FNO2S: C, 58.85; H, 4.56; N, 5.28; S,
12.09. Found: C, 59.01; H, 4.62; N, 5.20; S, 12.40.
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4.3.23. Compound 3l. Rf 0.28 (hexane–ethyl acetate, 2:1);
mp 155–1568C; 1H NMR (CDCl3, 400 MHz) d 7.76 (d, 2H,
J¼8 Hz), 7.52–7.48 (m, 2H), 7.26 (d, 2H, J¼8 Hz), 6.76 (t,
1H, J¼8 Hz), 4.27 (br, s, 2H, –NH2), 2.38 (s, 3H); 13C
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C, 59.03; H, 4.56; N, 4.99; S, 12.26.
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This work was supported by a grant (R04-2000-000-00015-
0) from Korea Science and Engineering Foundation.
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