Indium mediated allylation of nitro group on nitrobenzene derivatives in aqueous media

Article abstract of DOI:10.1081/SCC-100104827

Indium mediated allylation of nitro group was first achieved with four allyl bromides in aqueous media. Nitro- benzenes bearing 3- and/or 4-substituent(s) gave mainly N,N-diallylated (I or I′) and/or N,O-diallylated (II) products by Method A. Allylation o

Full text of DOI:10.1081/SCC-100104827

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
INDIUM MEDIATED ALLYLATION OF NITRO GROUP
ON NITROBENZENE DERIVATIVES IN AQUEOUS
MEDIA
Kyung Ho Kang , Kyung Il Choi , Hun Yeong Koh , Youseung Kim , Bong Young
Chung & Yong Seo Cho
To cite this article: Kyung Ho Kang , Kyung Il Choi , Hun Yeong Koh , Youseung Kim , Bong
Young Chung & Yong Seo Cho (2001) INDIUM MEDIATED ALLYLATION OF NITRO GROUP
ON NITROBENZENE DERIVATIVES IN AQUEOUS MEDIA, Synthetic Communications, 31:15,
2277-2286, DOI: 10.1081/SCC-100104827
To link to this article: http://dx.doi.org/10.1081/SCC-100104827
Published online: 09 Nov 2006.
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Date: 12 May 2017, At: 02:38

SYNTHETIC COMMUNICATIONS, 31(15), 2277–2286 (2001)
INDIUM MEDIATED ALLYLATION OF
NITRO GROUP ON NITROBENZENE
DERIVATIVES IN AQUEOUS MEDIA
Kyung Ho Kang,1 Kyung Il Choi,1 Hun Yeong Koh,1
Youseung Kim,1 Bong Young Chung,2 and
Yong Seo Cho1,
*
1Biochemicals Research Center, Korea Institute of
Science and Technology, P.O. Box 131,
Cheongryang, Seoul 130-650, S. Korea
2Department of Chemistry, Korea University,
Seoul 136-701, S. Korea
ABSTRACT
Indium mediated allylation of nitro group was first achieved
with four allyl bromides in aqueous media. Nitro- benzenes
bearing 3- and/or 4-substituent(s) gave mainly N,N-diallylated
(I or I0) and/or N,O-diallylated (II) products by Method A.
Allylation of nitrobenzenes having 2- (and 5-) substituent(s)
could be achieved only with crotyl bromide by Method B.
Nitrobenzene derivatives are useful intermediates in organic chemistry
since the nitro group can easily be converted to various functional groups
(e.g., amino, nitroso, hydroxyamino, etc.). Particularly they have been
* Corresponding author. Fax: þ82-2-958-5189; E-mail: ys4049@kist.re.kr
2277
Copyright & 2001 by Marcel Dekker, Inc.
www.dekker.com

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2278
KANG ET AL.
transformed most frequently into aminobenzenes by numerous reduction
methods.1
To the best of our knowledge, however, little is known for the
allylation reactions of the nitro group. G. Bartoli and co-workers reported
the allylation of nitro compounds using allyl magnesium chloride, where,
in situ treatment of the unstable intermediate, allyl adduct, with LiAlH4 in
the presence of Pd/C gave N-allyl-N-phenylhydroxyamine or N-allylamine.2
Recently, with the increasing environmental concerns, organic reac-
tions in aqueous media have constituted an interesting research area.3 Of the
reagents utilized under the concept, indium might be the most extensively
studied one owing to its capability of performing single electron transfer
(SET) process, and inertness to air and water.4 Here we wish to report
allylation reactions of nitro group with allyl bromides using indium metal
in aqueous media.
Scheme 1.
We have studied the N-allylation reaction of nitrobenzenes with allyl
bromides using indium in aqueous media, either with (Method A) or with-
out a base (Method B) (Scheme 1).
The allylation reaction showed strong dependence both on the posi-
tion of substituent(s) on the phenyl ring and the allyl bromide used.
Allylation reactions of nitrobenzenes bearing 3- and/or 4-substituent(s)
were achieved with allyl bromide (6.0 eq.) and indium (3.0 eq.) at 70ꢀC in
aqueous CH3CN (H2O/CH3CN ¼ 3/1, v/v) (Method A). Under this con-
dition the pH of the reaction mixture was around 2 due to the partial
decomposition of allyl bromide. The results are summarized in Table 1.
Allylation products varied according to the allyl bromide used.
In case of 3-bromopropene (Entry 1 ꢁ 5) and 3- bromo-2-methyl-
propene (Entry 11 ꢁ 15), products I (N,N-diallylated) and II (N,O-dially-
lated) were obtained as major in 12 ꢁ 54% and 34 ꢁ 89% yield, respectively.
Entry 11 and 12 exhibited far better yields compared to the others.
Interestingly, allylation reaction of nitrobenzenes with crotyl bromide

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2279
Table 1. Allylation of 3- and/or 4-Substituted Nitrobenzenes by Method A
Entry
R
R1
R2
R3
Productsa
Time (h)
Yield (%)b
51
1
H
4-F
I:II ¼ 16:1
I
I
12
1325
14
12
1323
2
2
2
2
2
2
34-CH
4
5
6
7
H
H
H
12
54
3
3,4-di-F
3-Cl
H
I:II ¼ 1:2
I:II ¼ 1:2.7
I:I0 ¼ 2.2:1
I:I0 ¼ 2.8:1
I:I0 ¼ 2:1
I:I0 ¼ 2.2:1
I:I0 ¼ 2.2:1
I:II ¼ 1.5:1
I:II ¼ 2:1
I:II ¼ 2.5:1
I:II ¼ 1:1
I:II ¼ 5:1
I:III ¼ 8:1
I
89
92
74
82
88
80
89
43
34
39
65
64
4-F
8
9
4-CH3
3,4-di-F
3-Cl
H
H
CH3
H
10
11
12
134-CH
14
15
16
17
18
19
20
2
4-F
1.5
14
1
12
1
0.4
2
0.5
1
H
H
CH3
3
3,4-di-F
3-Cl
H
4-F
4-CH3
3,4-di-F
3-Cl
c
–
CH3
CH3
H
–
I:III ¼ 3:1
41
57
I:III ¼ 1:1
aRatios were determined by HPLC and 1H NMR; bIsolated yields; entry 6 ꢀ 10:
c
determined by GC-Mass; No product could be found.
(Entry 6 ꢁ 10) produced N,N-diallylated products I and I0 in high yields
(74 ꢁ 92%) without N,O-diallylated product II. Finally, allylation with
4-bromo-2-methyl-2-butene (Entry 16 ꢁ 20) gave N,N-diallylated I and
N-monoallylated III.
Another series of nitrobenzenes having 2- (and 5-) substituent(s)
underwent the allylation reaction [allyl bromide (5.0 eq.) and indium
(2.0 eq.) at rt in aqueous CH3CN(H2O/CH3CN ¼ 3/1, v/v)] only in the pres-
ence of a base (Method B) (Table 2). When we attempted allylation of
2-chloronitrobenzene with crotyl bromide by Method A, no distinct spot
worth separation was observed on TLC. Only by adding a base we could

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KANG ET AL.
Table 2. Allylation of 2- (and 5-) Substituted Nitrobenzenes by Method B
Entry
R
Time (h)
Yield (%)a
Recovered S.M. (%)
1
2
2-Cl-
2-CH3-
10
12
10
10
50
23
3
8
3
32-Cl-5-CF
4
-
1
3
8
3
2-Cl-5-Cl-
62
find a clear spot, which later was identified as N-monoallylated compound
IV. Other bases than Cs2CO3 were less effective in facilitating the reaction.5
The pH was around 4 during the course of the reaction. The solvent system,
aqueous CH3CN, gave the best result of the ones applied, e.g., aqueous
THF, THF, DMF, or H2O. But, other allyl bromides reacted failed to
provide the N-monoallylated product under the same reaction condition.6
Based solely on these results, this reaction seemed to be very specific to both
2-substituted benzene and crotyl bromide.
In conclusion, indium mediated allylation of nitro group was first
achieved with allyl bromides in aqueous media. In cases of 3- and/or
4-substituted nitrobenzenes, N,N-diallylated product I or I0, N,O-diallylated
product II and N-monoallylated product III were obtained depending on
the used allyl bromides by Method A. Allylation of 2- (and 5-) substituted
nitrobenzenes could be achieved only with crotyl bromide by Method B
showing a very high specificity of the reaction.
EXPERIMENTAL
1H NMR spectra were obtained on a Varian Gemini 300 and Bruker
Avance 300 spectrometers. Chemical shifts were reported in ppm. Infrared
spectra were obtained on a Perkin Elmer 16FPC FT-IR spectrometer.
HRMS spectra were obtained on a JMS-HX 110A/HX110A (Jeol) spectro-
meter. Analytical thin layer chromatographies (TLC) were carried out on
precoated silica gel plates (Merk Kieselgel 60F254, layer thickness 0.25 mm).
Flash column chromatographies were conducted with silica gel grade
230–400 mesh (Merk Kieselgel 60 Art 9385).

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INDIUM MEDIATED ALLYLATION
General Procedure by Method A
2281
Nitrobenzene (0.14 g, 1.17 mmol), an allyl bromide (7.06 mmol) and
indium (405 mg, 3.53 mmol) were dissolved in 3 mL of aqueous solvent
(H2O-CH3CN/3:1/v:v). The reaction mixture was stirred for an appropriate
time period at 70ꢀC and extracted with diethyl ether. The organic layer was
washed with H2O, saturated NaHCO3, and brine, dried with MgSO4, and
concentrated in vacuo to give crude products. Column chromatographic
separation afforded the corresponding pure products characterized below.
1
N,N-Diallylaniline (1I): H NMR (300 MHz, CDCl3) d 3.99 (4H, d,
4.5 Hz), 5.22 (2H, d, J ¼ 3.3 Hz), 5.90 (2H, m), 6.67–6.82 (3H, overlap H),
7.25 (2H, t, J ¼ 8.5 Hz); 13C NMR (75 MHz, CDCl3) d 53.5, 113.1, 116.7,
117.0, 129.7, 134.8; HRMS EIþ, calcd for C12H15N 173.1204, found
173.1207.
N,O-Diallyl-N-phenylhydroxylamine (1II): 1H NMR (300 MHz, CDCl3)
d 3.94 (2H, d, J ¼ 7.2 Hz), 4.31 (2H, d, J ¼ 6.99 Hz), 5.18 (d, 2H, d,
J ¼ 8.55 Hz), 5.25 (2H, d, J ¼ 16.8 Hz), 6.0 (2H, overlap m), 6.99 (1H, t,
J ¼ 5.0 Hz), 7.06 (2H, d, J ¼ 8.58 Hz), 7.29 (2H, t, J ¼ 8.19 Hz); 13C NMR
(75 MHz, CDCl3) d 62.1, 75.2, 117.6, 118.8, 122.9, 129.5, 160.7, 162.5;
HRMS CIþ, calcd for C12H15NO 189.1154, found 190.1227.
1
N,N-Diallyl-4-fluoroaniline (2I): H NMR (300 MHz, CDCl3) d 3.90
(4H, d, J ¼ 4.89 Hz), 2.23(2H, d, J ¼ 1.71 Hz), 5.17 (2H, d, J ¼ 3.21 Hz); 5.88
(2H, m), 6.67 (2H, m), 6.92 (2H, m); 13C NMR (75 MHz, CDCl3) d 54.1,
114.4, 115.9, 116.0, 116.8, 134.8; 146.1, 156.8; HRMS EIþ, calcd for
C12H14FN 191.1110, found 191.1119.
1
N,N-Diallyl-p-toluidine (3I): H NMR (300 MHz, CDCl3) d 2.34 (3H,
s), 3.98 (4H, d, J ¼ 4.74 Hz), 5.24 (4H, overlap m), 5.94 (2H, overlap m), 6.72
(2H, d, J ¼ 8.73Hz), 7.11 (2H, d, J ¼ 8.46 Hz); 13C NMR (75 MHz, CDCl3) d
20.8, 53.6, 113.5, 116.5, 126.2, 130.2, 135.0, 147.3; HRMS EIþ, calcd for
C13H17N 187.2808, found 187.1353.
N,N-Diallyl-3,4-difluoroaniline (4I): 1H NMR (300 MHz, CDCl3) d
3.87 (4H, overlap d, J ¼ 4.74 Hz), 5.15 (2H, d, J ¼ 7.35 Hz), 5.19 (2H, d,
J ¼ 1.65 Hz), 5.86 (2H, overlap m), 6.35 (1H, m), 6.47 (1H, m), 6.96 (1H,
q, J ¼ 9.27 Hz); 13C NMR (75 MHz, CDCl3) d 54.0, 102.1, 102.2, 108.2,
117.1, 117.7, 117.8, 134.1 HRMS EIþ, calcd for C12H13F2N 209.1016,
found 209.1020.
N,O-Diallyl-N-(3,4-difluorophenyl)hydroxylamine (4II): 1H NMR
(300 MHz, CDCl3) d 3.87 (2H, d, J ¼ 6.27 Hz), 4.27 (2H, d, J ¼ 6.09 Hz),
5.34 (4H, overlap m), 5.97 (2H, m), 6.73 (1H, m), 6.95 (1H, m), 7.05 (1H,
q); 13C NMR (75 MHz, CDCl3) d 62.3, 75.2, 107.3, 117.6, 119.3, 133.6,
134.0, 143.2, 151.5; HRMS CIþ, calcd for C12H13F2NO 225.0965, found
226.1036.

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KANG ET AL.
N,N-Diallyl-3-chloroaniline (5I): H NMR (300 MHz, CDCl3) d 3.93
1
(4H, overlap d, J ¼ 4.68 Hz), 5.15 (2H, d, J ¼ 6.36 Hz), 5.19 (2H, d,
J ¼ 1.02 Hz), 5.86 (2H, overlap m), 6.57 (1H, d, J ¼ 2.52 Hz), 6.67 (2H, over-
lap d, J ¼ 6.39 Hz), 7.12 (1H, t, J ¼ 8.19 Hz); 13C NMR (75 MHz, CDCl3) d
53.4, 111.1, 112.9, 116.9, 130.6, 134.0, 134.2, 135.6, 150.4; HRMS EIþ, calcd
for C12H14ClN 207.0815, found 207.0814.
N,O-Diallyl-N-(3-chlorophenyl)hydroxylamine (5II): 1HNMR (300 MHz,
CDCl3) d 3.94 (2H, d, J ¼ 6.3Hz), 4.30 (2H, d, J ¼ 6.0 Hz), 5.22 (2H, t,
J¼ 9.6Hz), 5.3 5 (2H, t, J¼ 17.9 Hz), 5.98 (2H, overlap m), 6.91 (2H, m),
7.09 (1H, s), 7.19 (1H, t, J¼ 8.01 Hz); 13C NMR (75 MHz, CDCl3) d 61.5,
75.3, 115.3, 117.3, 119.2, 122.6, 130.5, 133.7, 134.0, 153.3, 166.5; HRMS
FAB(MþH)þ, calcd for C12H14ClNO 223.0763, found 224.0841.
N,N-Bis-(2-methylpro-2-enylaniline (11I): 1H NMR (300 MHz, CDCl3)
d 1.75 (6H, s), 3.82 (4H, s), 4.80 (2H, s, gem Ha, J ¼ 19.1 Hz), 4.86 (2H, s,
gem Hb), 6.66 (3H, m, phenyl), 7.19 (2H, t, J ¼ 1.47 Hz, phenyl); 13C NMR
(75 MHz, CDCl3) d 20.4, 56.7, 110.7, 112.3, 116.4, 129.3, 141.1, 149.3;
HRMS EIþ, calcd for C14H19N 201.1517, found 201.1514.
N,O-Bis-(2-methylprop-2-enyl)-N-phenylhydroxylamine(11II):1H NMR
(300 MHz, CDCl3) d 1.81 (3H, s), 1.88 (3H, s), 3.83 (2H, s), 4.22 (2H, s), 4.93
(2H, s), 5.02 (2H, d), 6.98 (1H, t), 7.10 (2H, m), 7.30 (2H, t, J ¼ 7.29 Hz); 13
C
NMR (75 MHz, CDCl3) d 20.8, 21.6, 66.6, 78.0, 114.2, 114.4, 117.1, 122.7,
129.4, 142.5, 152.6; HRMS FAB (M þ H)þ, calcd for C14H19NO 217.1467,
found 218.1540.
N,N-Bis(2-methylprop-2-enyl)-4-fluoroaniline (12I): 1H NMR (300 MHz,
CDCl3) d 1.74 (6H, s), 3.78 (4H, s), 4.79 (2H, s), 4.86 (2H, s), 6.54 (2H, m),
6.88 (2H, m); 13C NMR (75 MHz, CDCl3) d 20.6, 57.7, 111.2, 113.6, 115.9,
141.5, 146.2, 156.6; HRMS EIþ, calcd for C14H18FN 219.1423, found
219.1413.
N,O-Bis(2-methylprop-2-enyl)-N-(4-fluorophenyl)hydroxylamine (12II):
1H NMR (300 MHz, CDCl3) d 1.78 (3H, s), 1.88 (3H, s), 3.74 (2H, s), 4.17
(2H, s), 4.92 (2H, s), 4.98 (1H, s), 5.00 (1H, s), 6.98 (2H, m), 7.10 (2H, m);
13C NMR (75 MHz, CDCl3), d 20.7, 21.7, 67.5, 77.9, 114.2, 114.8, 115.8,
116.0, 119.8, 119.8, 141.9, 142.3, 148.9, 158.8, 160.4; HRMS FAB(M þ H)þ,
calcd for C14H18FNO 235.1372, found 236.1460.
1
N,N-Bis-(2-methylprop-2-enyl)-p-toluidine (13I): H NMR (300 MHz,
CDCl3) d 1.75 (6H, s), 2.25 (3H, s), 3.80 (4H, s), 4.80 (2H, s), 4.86 (2H, s),
6.57 (2H, d, J ¼ 6.99 Hz), 7.01 (2H, d, J ¼ 7.68 Hz); 13C NMR (75 MHz,
CDCl3) d 20.6, 20.8, 57.2, 111.0, 112.8, 125.7, 130.1, 141.7, 147.5; HRMS
EIþ, calcd for C15H21N 215.1674, found 215.1674.
N,O-Bis-(2-methylprop-2-enyl)-N-(4-methylphenyl)hydroxylamine
(13II): 1H NMR (300 MHz, CDCl3) d 1.79 (3H, s), 1.88 (3H, s), 2.31 (3H, s),
3.76 (2H, s), 4.18 (2H, s), 4.92 (2H, s), 5.00 (2H, s), 7.01 (2H, d, J ¼ 8.0 Hz),

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INDIUM MEDIATED ALLYLATION
2283
7.11 (2H, d, J ¼ 7.29 Hz); 13C NMR (75 MHz, CDCl3) d 20.8, 21.2, 21.7,
67.2, 77.9, 114.0, 114.4, 118.0, 130.0, 132.5, 142.1, 142.7, 150.4; HRMS
FAB(M þ H)þ, calcd. for C15H21NO 231.1623, found 232.1709.
N,N-Bis(2-methylprop-2-enyl)-3,4-difluoroaniline (14I): 1H NMR
(300 MHz, CDCl3) d 1.79 (6H, s, -CH3) 3.76 (4H, s, -CH2-), 4.76 (2H, s,
-C ¼ CHaHb), 4.87 (2H, s, -C ¼ CHaHb), 6.23(1H, m), 6.38 (1H, m), 6.94
(1H, q); HRMS EIþ, calcd for C14H17F2N 237.1329, found 237.1326.
N,O-Bis(2-methylprop-2-enyl)-N-(3,4-difluorophyenyl)hydroxylamine
(14II): 1H NMR (300 MHz, CDCl3) d 1.79 (3H, s, -CH3), 1.85 (3H, s, -CH3),
3.76 (2H, s, -N-CH2-), 4.17 (2H, s, -N-O-CH2-), 4.93(2H, s, overlap
-C ¼ CHaHb), 4.99 (1H, s, -C ¼ CHaHb), 5.00 (2H, s, -C ¼ CHaHb), 6.71
(1H, m), 6.96 (1H, m), 7.06 (1H, q, J ¼ 9.6 Hz); HRMS FAB(M þ H)þ,
calcd for C14H17F2NO 253.1278, found 252.1190.
N,N-Bis-(2-methylprop-2-enyl)-3-chloroaniline (15I): 1H NMR
(300 MHz, CDCl3) d 1.73(6H, s), 3.78 (4H, s), 4.76 (2H, s), 4.85 (2H, s),
6.48 (1H, dd, J ¼ 2.46 Hz, 2.28 Hz), 6.57 (1H, s), 6.58 (1H, d, J ¼ 0.84 Hz),
7.05 (1H, t, J ¼ 7.95 Hz); HRMS EIþ, calcd for C14H18ClN 235.1128, found
235.1130.
N,O-Bis-(2-methylprop-2-enyl)-N-(3-chlorophenyl)hydroxylamine (15II):
1H NMR (300 MHz, CDCl3) d 1.81 (3H, s), 1.85 (3H, s), 3.84 (2H, s),
4.21 (2H, s), 4.95 (2H, s), 5.00 (1H, s), 5.03(1H, s), 6.91 (2H, t,
J ¼ 7.71 Hz), 7.07 (1H, s), 7.19 (1H, t, J ¼ 8.04 Hz); 13C NMR (75 MHz,
CDCl3) d 20.8, 21.6, 65.9, 78.2, 114.5, 114.8, 115.0, 116.9, 122.3, 130.4,
135.3, 141.5, 142.0, 153.8; HRMS FAB(M þ H)þ, calcd for C14H18ClNO
251.1077, found 252.1157.
N,N-Bis-(3-methylbut-2-enyl)aniline (16I): 1H NMR (300 MHz, CDCl3)
d 1.73(6H, s), 1.75 (6H, s), 3.90 (4H, d, J ¼ 6.27 Hz, overlap), 5.25 (2H, m,
overlap, -CH2-), 6.73(3H, dt, overlap, J ¼ 8.25 Hz), 7.24 (2H, t, J ¼ 7.41,
benzene); HRMS EIþ, calcd for C16H23N 229.1830, found 229.1825.
1
N-(3-Methylbut-2-enyl)aniline (16III): H NMR (300 MHz, CDCl3) d
1.71 (3H, s), 1.75 (3H, s), 3.69 (2H, d, J ¼ 6.6 Hz, -CH2-), 5.35 (1H, m,
-CH ¼ ), 6.62 (2H, d, J ¼ 2.4 Hz), 6.72 (1H, t, J ¼ 7.44 Hz), 7.19 (2H, t,
J ¼ 8.31 Hz); HRMS EIþ, calcd for C11H15N 161.1204, found 161.1210.
N,N-Bis-(3-methylbut-2-enyl)-4-fluoroaniline (17I): 1H NMR (300 MHz,
CDCl3) d 1.67 (6H, s), 1.72 (6H, s), 3.84 (4H, d, overlap, -CH2-), 5.20 (2H,
m, -CH ¼ ), 6.75 (2H, m), 6.93(2H, t, J ¼ 9.12 Hz); HRMS EIþ, calcd for
C16H22FN 247.1736, found 247.1744.
N,N-Bis-(3-methylbut-2-enyl)-3,4-difluoroaniline (19I): 1H NMR
(300 MHz, CDCl3) d 1.69 (6H, s), 1.73(6H, s), .380 (4H, d, J ¼ 6 Hz,
-CH2-, overlap), 5.15 (2H, m, -CH ¼ ), 6.31 (1H, m), 6.40 (1H, m), 6.95
(1H, dd, J ¼ 9.3Hz); HRMS EI þ, calcd for C16H21N 265.1642, found
265.1634.

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KANG ET AL.
N-(3-Methylbut-2-enyl)-3,4-difluoroaniline (19III): 1H NMR (300 MHz,
CDCl3) d 1.70 (3H, s), 1.79 (3H, s), 3.80 (2H, d, J ¼ 6.27 Hz), 5.15 (1H, m),
6.33 (1H, m), 6.47 (1H, m), 6.7 (1H, dd, J ¼ 9.36 Hz); HRMS EIþ, calcd for
C11H13F2N 197.1016, found 197.1011.
N,N-Bis-(3-Methylbut-2-enyl)-3-chloroaniline(20I):1HNMR(300 MHz,
CDCl3) d 1.70 (6H, s), 1.73(6H, s), 1.73(6H, s), 3.84 (4H, d, J ¼ 6.21 Hz,
-CH2-), 5.16 (2H, m, -CH ¼ ), 6.54 (1H, m), 6.63(2H, m), 7.09 (1H, t,
J ¼ 7.95 Hz); HRMS EIþ, calcd for C16H22ClN 263.1441, found 263.1435.
N-(3-Methylbut-2-enyl)-3-chloroaniline (20III): 1H NMR (300 MHz,
CDCl3) d 1.73 (3H, s), 1.77 (3H, s), 3.67 (2H, d, J ¼ 6.81 Hz), 5.31 (1H,
m, -CH ¼ ), 6.48 (1H, m), 6.59 (1H, d, J ¼ 2.8 Hz), 6.69 (1H, d,
J ¼ 2.8 Hz), 7.09 (1H, t, J ¼ 8.04 Hz); HRMS EIþ, calcd for C11H14ClN
195.0815, found 195.0820.
N,N-Dicrotylaniline (6I): calcd. for C14H19N 201.1517, found 201.10.
N-(But-2-enyl)-N-(1-methylprop-2-enyl)aniline (6I0): calcd. for C14H19N
201.1517, found 201.10.
N,N-Dicrotyl-4-fluoroaniline (7I): calcd. for C14H18FN 219.1423, found
219.10.
N-(But-2-enyl)-N-(1-methylprop-2-enyl)-4-fluroaniline) (7I0): calcd. for
C14H18FN 219.1423, found 219.10.
N,N-Dicrotyl-p-toluidine (8I): calcd. for C15H21N 215.1674, found
215.15.
N-(But-2-enyl)-N-(1-methylprop-2-enyl)-p-toluidine (8I0): calcd. for
C15H21N 215.1674, found 215.15.
N,N-Dicrotyl-3,4-difluoroaniline (9I): calcd. for C14H17F2N 237.1329,
found 237.15.
N-(But-2-enyl)-N-(1-methylprop-2-enyl)-3-chloroaniline (9I0): calcd. for
C14H17F2N 237.1329, found 237.15.
N,N-Crotyl-3-chloroaniline (10I): calcd. for C14H18CIN 235.1128,
found 235.15.
N-(But-2-enyl)-N-(1-methylprop-2-enyl)-3-chloroaniline (10I0): calcd.
for C14H18CIN 235.1128, found 235.15.
General Procedure by Method B
A nitrobenzene (1.15 mmol), crotyl bromide (5.75 mmol), indium
(2.30 mmol) and Cs2CO3 (2.30 mmol) were dissolved in 3 mL of aqueous
solvent (H2O-CH3CN/3:1/v:v). The reaction mixture was stirred for about
12 h at rt and extracted with diethyl ether. Following an ordinary work-up
procedure as in Method A, were obtained the compounds characterized
below.

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2285
N-(1-Methylprop-2-enyl)-chlorophenylhydroxylamine (Entry 1, Table 2):
1H NMR (300 MHz, CDCl3) d 1.25 (3H, d, J ¼ 6.66 Hz), 3.94 (1H, m), 5.06
(2H, dd, J ¼ 10.4 Hz, J ¼ 17.3Hz), 5.98 (1H, m), 7.01 (1H, t, J ¼ 7.8 Hz), 7.22
(1H, t, J ¼ 8.16 Hz), 7.26 (1H, t, J ¼ 14.1 Hz), 7.56 (1H, d, J ¼ 6.6 Hz); IR
(film, cmꢂ1) 3210 (-OH); EI-MS, calcd for C11H13ClNO 196.6730, found
197.05.
N-(1-Methylprop-2-enyl)-2-methylphenylhydroxylamine (Entry 2, Table
2): 1H NMR (300 MHz, CDCl3) d 1.23(3H, d, J ¼ 6.6 Hz), 2.28 (3H, s), 3.63
(1H, m), 5.09 (2H, dd, J ¼ 3.84 Hz, J ¼ 13.7 Hz), 5.45 (1H, br s), 6.02 (1H,
m), 7.03(1H, t, J ¼ 7.35 Hz), 7.13 (1H, d, J ¼ 14.2 Hz), 7.22 (1H, t,
J ¼ 7.35 Hz), 7.47 (1H, d, J ¼ 8.04 Hz).
N-(1-Methylprop-2-enyl)-2-chloro-5-trifluoromethylphenylhydroxyl-
amine(Entry3,Table2):1HNMR(300 MHz,CDCl3)d1.30(3H,d,J ¼ 6.66 Hz),
3.98 (1H, m), 5.07 (2H, dd, J ¼ 10.4 Hz, J ¼ 17.3Hz), 5.97 (1H, m), 6.53(1H,
br s), 7.20 (1H, d, J ¼ 8.31 Hz), 7.35 (1H, d, J ¼ 8.46 Hz), 7.77 (1H, s).
N-(1-Methylprop-2-enyl)-2-chloro-5-trifluoromethylphenylhydroxyl-
amine (Entry 4, Table 2): 1H NMR (300 MHz, CDCl3) d 1.26 (3H, d,
J ¼ 6.63Hz), 3.97 (1H, m), 5.04 (2H, dd, J ¼ 9.7 Hz, J ¼ 13Hz), 5.99 (1H, m),
7.22 (1H, d, J ¼ 8.2 Hz), 7.30 (1H, d, J ¼ 8.45 Hz), 7.63(1H, s).
ACKNOWLEDGMENTS
This project was financially supported by the Korea Ministry of
Science and Technology.
REFERENCES
1. (a) He, Y.; Zhao, H.; Pan, X.; Wang, S. Synth. Commun. 1989, 19,
3047. (b) Ayyanger, N.R.; Brahme, K.C.; Kalkote, U.R.; Srinivasan,
K.V. Synthesis 1984, 938. (c) Davies, R.R.; Hodgson, H.H. J. Chem.
Soc. 1943, 281. (d) Nishimura, S. Bull. Chem. Soc. Jpn. 1961, 34, 3 2.
(e) Corbett, J.F. Chem. Commun. 1968, 1257. (f) Nystrom, R.F.;
Brown, W.G. J. Am. Chem. Soc. 1948, 70, 3739. (g) Reductions in
Organic Chemistry, 2nd ed.; Milos Hudlicky, ACS Monograph 188.
pp. 91–101, Ed.; American Chemical Society, 1996.
2. (a) Bartoli, G.; Marcantoni, E.; Bosco, M.; Dalozzo, R. Tetrahedron
Letters 1988, 29, 2251. (b) Bartoli, G.; Marcantoni, E.; Petrini, M.
J. Org. Chem. 1990, 55, 4456. (c) Bartoli, G.; Marcantoni, E.; Petrini,
M. J. Chem. Soc. Chem. Commun. 1991, 12, 793.

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KANG ET AL.
3. Organic Synthesis in Water, Paul A. Grieco, Ed.; Blackie Academic &
Professional, UK, 1998.
4. (a) Organic Reactions in Aqueous Media, Li, C.-J.; Chan, T.-H. John
Wiley & Sons, INC, 1997. (b) Li, C.-J.; Chan, T.-H. Tetrahedron. 1999,
55, 11149. (c) Cintas, P. Synlett 1995, 1087.
5. Several bases (e.g. diisoprophyl ethylamine, pyridine, DBU, K2CO3,
CaCO3 etc) were tried.
6. When Entries 6 and 7 in Table 1 were reacted by Method B, N,N-
diallylated products I and II were observed in 56% (I:II ¼ 1.6:1) and
51% (I:II ¼ 1.3:1) yield, respectively.
Received in Japan July 25, 2000

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