Ring opening of epoxides and aziridines with sodium azide using Oxone in aqueous acetonitrile: A highly regioselective azidolysis reaction1

Article abstract of DOI:10.1055/s-2002-34848

A wide variety of epoxides and aziridines were converted to the corresponding β-azido alcohols and β-azido amines with sodium azide using Oxone in aqueous acetonitrile. The reactions were highly regioselective and efficient with excellent yields at room t

Full text of DOI:10.1055/s-2002-34848

2
254
PAPER
®
Ring Opening of Epoxides and Aziridines with Sodium Azide using Oxone
in Aqueous Acetonitrile: A Highly Regioselective Azidolysis Reaction1
R
G
ing Opening of
E
o
poxides and
w
Aziridines
w
ith So
r
dium
A
a
zide varam Sabitha,* R. Satheesh Babu, M. Shashi Kumar Reddy, J. S. Yadav
Organic Division I, Indian Institute of Chemical Technology, Hyderabad 500 007, India
Received 16 March 2002; revised 26 July 2002
12
ring-opening reaction of aziridines with TMSN . Yeung
3
Abstract: A wide variety of epoxides and aziridines were convert-
17
and co-workers reported the chromium complex mediat-
ed ring-opening reaction of aziridines with TMSN .
ed to the corresponding -azido alcohols and -azido amines with
®
sodium azide using Oxone in aqueous acetonitrile. The reactions
3
1
8
Transition metal-based complexes were also used when
N-benzoylaziridines were the substrates, but the rear-
rangement to oxazolines took place. As part of a pro-
gramme aimed at the synthesis of epoxides and aziridines
and their applications in organic synthesis, we have stud-
ied the ring opening reactions of these small heterocyclic
compounds.19
were highly regioselective and efficient with excellent yields at
room temperature under mild reaction conditions.
®
Keywords: Oxone , epoxides, aziridines, azides, regioselectivity
2
3
Epoxides and aziridines are among the most useful syn-
thetic intermediates in organic synthesis. Due to their
three membered ring strain, they undergo facile, regio- We recently found that potassium peroxymonosulfate,
®
and stereoselective ring-opening reactions with various commonly sold as Oxone (2 KHSO , KHSO , K SO )
5
4
2
4
nucleophiles, yielding a broad range of valuable prod- catalyze in an extraordinarily effective way the
4
,5
20
ucts. Among these, the azidolysis of epoxides and azir- alcoholysis of epoxides and aziridines in aqueous meth-
idines enjoys a prominent position for the preparation of anol. On this basis, we looked for an analogous catalysis,
6
7
azido alcohols and azido amines, respectively. The vici- which could be efficient in the azidolysis of epoxides and
nal azido alcohols are precursors of amino alcohols8 aziridines, since Oxone is inexpensive, safe and readily
which are well known as -blockers and a common struc- available oxidizing agent. Recently we have also found a
tural components in a vast group of natural products. Fur- very useful method for easy azidolysis of epoxides and
ther, they have also been utilized in carbohydrate aziridines with NaN in the presence of CeCl . Herein, we
chemistry or in the chemistry of nucleosides. The azi- wish to report a novel, convenient and highly efficient
do amines obtained upon ring opening are easily trans- method for the regioselective azidolysis of epoxides and
formed to valuable vicinal diamines. The classical aziridines with NaN in the presence of Oxone in aque-
®21
9
22
3
3
1
0
11
1
2
®
3
reagents for azidohydrin synthesis are the combined use ous acetonitrile (Schemes 1 and 2).
of TMSN or NaN and a Lewis acid or a transition metal
3
3
1
3
complex. In most of epoxide ring-opening reactions
with NaN under either alkaline or acidic conditions, suf-
3
fer from high temperatures or long reaction times. In ad-
dition to these, side reactions, isomerizations,
epimerization and rearrangements have also observed by
the alkaline conditions of the reaction. It has been
found that NaN impregnated on a calcium cation ex-
3
Scheme 1
change Y-type Zeolite induces the nucleophilic ring
opening of epoxides in protic solvents affording azidohy-
1
4
drins. Other reported reagents are tributyltinazide and
1
5
16
dibutyltinazide, in DMF. Use of phase transfer catalyst
has also been reported recently for the preparation of azi-
dohydrins. Even though several procedures have appeared
for the ring opening of epoxides, a limited number of
methods have been available for the ring-opening reac-
tions of aziridines. The most straightforward route to azi-
do amines involves the regioselective ring opening of
aziridines with TMSN in the presence of a promoter.
3
Tetrabutylammonium fluoride was found to promote the
Scheme 2
The reaction of styrene oxide (Table 1, Entry 8) with
Synthesis 2002, No. 15, Print: 29 10 2002.
Art Id.1437-210X,E;2002,0,15,2254,2258,ftx,en;Z04502SS.pdf.
NaN in aqueous acetonitrile was studied at room temper-
ature in the presence of Oxone . The reaction was found
3
®
©
Georg Thieme Verlag Stuttgart · New York
ISSN 0039-7881

PAPER
Ring Opening of Epoxides and Aziridines with Sodium Azide
2255
®
to be completed within 30 minutes and it proceeded in a of Oxone afforded a major isomer resulting by the attack
regiospecific manner, whereby azide ion attacked exclu- of azide ion at the benzylic position, with a small amount
sively at benzylic position as expected. This reaction also of the other isomer. The reaction was found to be highly
produced a very small percentage of the other isomer. The efficient and completed within 90 minutes at room tem-
ring opening reactions of 3-phenoxy-1,2-epoxy propanes perature giving a overall yield of 98%. As in the case of
(
Table 1, Entries 9–12), epichlorohydrin and isopropyl epoxides, the terminal aliphatic aziridines (Table 2, En-
glycidyl ether were found to be highly regioselective af- tries 8–10) yielded a mixture of products. The formation
fording single products resulting from the terminal attack of the major isomer resulting from the attack of azide ion
of azide ion. In the case of aliphatic terminal epoxides at terminal carbon atom and the minor isomer obtained by
(
Table 1, Entries 2 and 3) the attack appears predominent- internal attack. These isomers could not be separated us-
ly at the terminal carbon atom of the epoxide ring. The ing column chromatography. Under similar conditions,
azido alcohols obtained using cycloalkene oxides cyclic aziridines (Table 2, Entries 5–7) gave trans prod-
(
Table 1, Entries 5, 6 and 7) were shown to possess a trans ucts and the structures were confirmed by coupling con-
1
configuration.
stants in H NMR spectroscopy. The azidolysis reaction
of 1-vinylcyclohexyl N-tosylaziridine (Table 2, Entry 4)
was found to be highly regioselective and gave only one
isomer exclusively by attack of azide ion at the terminal
carbon atom of the aziridine ring.
Similarly, treatment of styrene N-tosylaziridine (Table 2,
Entry 1) with NaN in aqueous acetonitrile in the presence
3
Table 1 Regioselective Ring Opening of Epoxides with NaN in the
Presence of Oxone
3
®
Entry Epoxide
Producta
Time
min)
Yield
(%)
Table 2 Regioselective Ring Opening of Aziridenes with NaN in
3
b
(
the Presence of Oxone®
1
2
3
4
120
120
120
120
95
Producta
Entry Aziridine
1
Time
Yield
(%)
b
(
min)
90 (4)
89 (3)
98
90
93 (5)
2
90
89 (6)
5
45
95
3
4
120
90
90 (5)
96
6
7
8
45
45
30
98
96
91 (4)
5
6
7
8
9
60
60
98
9
90
90
97
95
94
10
60
96
1
1
1
120
90
94
180
240
180
89 (2)
90 (2)
94 (3)
2
3
96
92
1
0
1
120
a
1
a
1
The products obtained were characterized by IR, H NMR and mass
The products obtained were characterized by IR, H NMR and mass
spectra.
spectra.
b
b
Yield refers to the isolated pure products after column chromatogra-
Yield refers to the isolated pure products after column chromatogra-
phy. Yields in parantheses corresponds to the other regioisomer (de-
termined by their crude NMR spectrum).
phy. Yields in parantheses corresponds to the other regioisomer (de-
termined by their crude NMR spectrum).
Synthesis 2002, No. 15, 2254–2258 ISSN 0039-7881 © Thieme Stuttgart · New York

2
256
G. Sabitha et al.
PAPER
®
+
In all the cases, 0.5 equivalents of Oxone was required MS (EI): m/z = 59 (M – CH
N ) .
3
2
for the complete conversion of the epoxides and aziridines
1
-Azido-2-hexanol (Table 1, Entry 3)
into the corresponding azido alcohols and azido amines
within a short period of time. Reducing the equivalents of
Liquid.
–
1
®
IR (neat): 2090, 3380 cm .
Oxone resulted in isolation of low yields of the products
along with the recovery of starting materials even after 1H NMR (200 MHz, CDCl
): = 0.80 (t, J = 7.2 Hz, 3 H, CH
),
3
3
1
.10–1.60 (m, 6 H, CH ), 1.85 (br s, 1 H, OH), 3.16–3.30 (m, 2 H,
prolonged reaction times. Ring opening reactions of ep-
2
CH N ), 3.55–3.80 (m, 1 H, CHOH).
2
3
oxides and aziridines with NaN carried out at room tem-
3
+
perature in the presence of KHSO and K SO did not give MS (EI): m/z = 87 (M – CH N ) .
4
2
4
2 3
ring opened products, instead giving recovery of the start-
ing materials. This clearly demonstrates the necessity of
1
-Azido-3-isopropoxy-2-propanol (Table 1, Entry 4)
Liquid.
KHSO to promote azidolysis. It was also found that the
5
–
1
IR (neat): 2100, 3385 cm .
present reaction is also applicable to the substrates having
oxidation sensitive functionalities like alkenes to afford 1H NMR (200 MHz, CDCl
): = 1.18 (s, 3 H, CH ), 1.20 (s, 3 H,
3
3
CH ), 2.45 (br s, 1 H, OH), 3.35 (d, 2 H, J = 4.4 Hz), 3.40–3.50 (m,
2
the product in excellent yields without any side products
Table 1, Entry 13). Even though at present the mecha-
3
H, OCH ), 3.60 (hep, 1 H, J = 5.0 Hz), 3.85 (m, 1 H, CHOH).
2
(
+
nism of the cleavage reaction is not known, it may be at- MS (EI): m/z = 103 (M – CH
N
) .
2
3
tributed to the mild acidic nature of the Oxone® in
2
-Azidocyclopentan-1-ol (Table 1, Entry 5)
aqueous acetonitrile which may be coordinated with oxy-
gen or nitrogen and facilitate the nucleophilic ring open-
ing of epoxides and aziridines.
Liquid.
–
1
IR (neat): 2105, 3390 cm .
1H NMR (200 MHz, CDCl
): = 1.24 (br s, 1 H, OH), 1.50–2.40
3
®
In conclusion, Oxone proved to be an excellent promoter
(
m, 6 H, CH ), 3.65–3.75 (q, 1 H, CHN ), 4.08–4.28 (q, 1 H,
2
3
for highly regioselective ring opening of epoxides and
aziridines to prepare azidohydrins and azido amines. The
advantages of the present protocol are the use of inexpen-
sive reagent, operational simplicity, easy work-up proce-
dures, high regioselectivity and isolation of pure products.
Further the short reaction times and the equal reaction ef-
ficiency for both epoxides and aziridines at room temper-
ature may open new entry into the ring opening reactions
in the field of synthetic organic chemistry.
CHOH).
+
MS (EI): m/z = 85 (M – N ) .
3
2
-Azidocyclohexan-1-ol (Table 1, Entry 6)
Liquid.
–
1
IR (neat): 2100, 3395 cm .
1
H NMR (200 MHz, CDCl ): = 1.20–1.55 (m, 3 H), 1.60–1.80 (m,
3
2
H), 1.90–2.30 (m, 3 H), 3.10–3.25 (m, 1 H), 3.30–3.45 (m, 1 H).
+
MS (EI): m/z = 99 (M – N ) .
3
2
-Azidocyclooctan-1-ol (Table 1, Entry 7)
Regioselective Opening of Epoxides and Aziridines Giving -
Azido Alcohols and -Azido Amines; General Procedure
Liquid.
–
1
IR (neat): 2095, 3390 cm .
1H NMR (200 MHz, CDCl
): = 1.20–1.55 (m, 3 H), 1.60–1.80 (m,
6 H), 1.90–2.30 (m, 3 H), 3.06–3.20 (m, 1 H), 3.24–3.35 (m, 1 H).
A mixture of epoxide or aziridine (1 mmol) in H O–MeCN (1:9, v/
2
v), and Oxone (0.5 mmol) was stirred for 5 min at r.t., then NaN (1
3
3
mmol) was added and the reaction mixture was stirred at r.t. for a
specified time (see Tables 1 and 2). After completion, as indicated
by TLC, the solvents were removed under reduced pressure and the
residue extracted with EtOAc (2 10 mL). The combined organic
layers were dried (Na SO ), concentrated and the residue was puri-
+
MS (EI): m/z = 127 (M – N ) .
3
2
-Azido-2-phenyl-1-ethanol (Table 1, Entry 8)
2
4
Liquid.
fied by column chromatography (silica gel; Merck, 100–200 mesh)
to afford the corresponding pure -azido alcohol or -amino alco-
hol.
–
1
IR (neat): 2100, 3380 cm .
1H NMR (200 MHz, CDCl3): = 2.00 (br s, 1 H, OH), 3.75 (d,
J = 6.5 Hz, 2 H, CH OH), 4.70 (t, J = 6.5 Hz, 1 H, CHN ), 7.20–
7.40 (m, 5 H, ArH).
2
3
1
-Azido-3-chloro-2-propanol (Table 1, Entry 1)
Liquid.
MS (EI): m/z = 162 (M – 1)+.
–
1
IR (neat): 2100, 3385 cm .
1
2-Azido-1-phenyl-1-ethanol
H NMR (200 MHz, CDCl ): = 2.40 (br s, 1 H, OH), 3.28–3.45
m, 4 H), 3.86 (m, 1 H, CHOH).
3
1
H NMR (200 MHz, CDCl ): = 2.55 (br s, 1 H, OH), 3.35–3.50
3
(
(
dd, J = 7.4, 5.5 Hz, 2 H, CH N ), 4.75–4.96 (m, 1 H, CHOH),
2
3
+
+
MS (EI): m/z = 59 (M – CH N ) , 79 (M – CH N ) .
2
3
2
3
7.20–7.40 (m, 5 H, ArH).
MS (EI): m/z = 163 (M – 1)+.
1
-Azido-2-butanol (Table 1, Entry 2)
Liquid.
1
-Azido-3-phenoxy-2-propanol (Table 1, Entry 9)
–
1
IR (neat): 2090, 3390 cm .
1H NMR (200 MHz, CDCl3): = 0.98 (t, J = 7.0 Hz, 3 H, CH3),
.40–1.65 (m, 2 H, CH ), 1.96 (br s, 1 H, OH), 3.15–3.45 (m, 2 H,
Liquid.
IR (neat): 2100, 3390 cm–1.
1
2
CH N ), 3.58–3.76 (m, 1 H, CHOH).
2
3
Synthesis 2002, No. 15, 2254–2258 ISSN 0039-7881 © Thieme Stuttgart · New York

PAPER
Ring Opening of Epoxides and Aziridines with Sodium Azide
2257
1H NMR (200 MHz, CDCl3): = 1.55 (br s, 1 H, OH), 3.70 (d,
1N-[2-Azido-2-(4-methylphenyl)ethyl]-4-methyl-1-benzene-
J = 6.5 Hz, 2 H, CH N ), 4.20 (d, J = 6.5 Hz, 2 H, OCH ), 4.65 (t,
sulfonamide (Table 2, Entry 2)
2
3
2
J = 6.5 Hz, 1 H, CHOH), 7.20–7.40 (m, 5 H, ArH).
Liquid.
MS (EI): m/z = 192 (M – 1)+.
IR (neat): 2100, 3370 cm–1.
1H NMR (200MHz, CDCl3): = 2.35 (s, 3 H, ArCH ), 2.45 (s, 3 H,
3
1
1
-Azido-3-(3,5-dimethylphenoxy)-2-propanol (Table 1, Entry
0)
ArCH ), 2.94–3.30 (m, 2 H, CH N ), 4.50–4.60 (dd, J = 7.8, 5.2 Hz,
3
2
3
1
H, CHNH), 4.90 (m, 1 H, NH), 7.10–7.20 (m, 4 H, ArH), 7.30 (d,
Liquid.
J = 8.4 Hz, 2 H, ArH), 7.75 (d, J = 8.4 Hz, 2 H, ArH).
–
1
IR (neat): 2100, 3390 cm .
1H NMR (200 MHz, CDCl3): = 1.48 (br s, 1 H, OH), 2.30 (s, 6 H,
+
MS (EI): m/z = 288 (M – N ) .
3
ArCH ), 3.50 (dd, J = 4.2, 4.6 Hz, 2 H, NCH ), 4.00 (d, J = 6.5 Hz,
1N-[2-Azido-1-(4-methylphenyl)ethyl]-4-methyl-1-benzene-
3
2
2
1
H, OCH ), 4.05–4.20 (m, 1 H, OCH), 6.55 (s, 2 H, ArH), 7.00 (s,
H, ArH).
sulfonamide
2
1
H NMR (200 MHz, CDCl3): = 2.30 (s, 3 H, ArCH ), 2.40 (s, 3 H,
3
MS (EI): m/z = 220 (M – 1)+.
ArCH
3
), 3.49 (d, J = 5.6 Hz, 2 H, CH
2 3
N ), 4.35–4.40 (dd, J = 11.8,
5
7
.6 Hz, 1 H, CHNH), 5.20 (m, 1 H, NH), 7.00–7.15 (m, 4 H, ArH),
.25 (d, J = 8.0 Hz, 2 H, ArH), 7.65 (d, J = 8.0 Hz, 2 H, ArH).
N-[2-Azido-2-(4-chlorophenyl)ethyl]-4-methyl-1-benzene-
1
1
-Azido-3-(3,5-dichlorophenoxy)-2-propanol (Table 1, Entry
1)
1
Liquid.
sulfonamide (Table 2, Entry 3)
IR (neat): 2100, 3390 cm .
1H NMR (200 MHz, CDCl3): = 2.45 (s, 3 H, ArCH ), 3.05–3.15
–
1
IR (neat): 2100, 3555 cm .
–1
1
H NMR (200MHz, CDCl3):
= 2.75 (br s, 1 H, OH), 3.80 (t,
3
J = 7.2 Hz, 2 H, CH N ), 4.12 (d, J = 6.8 Hz, 2 H, OCH ), 4.15–4.30
2
3
2
(m, 1 H), 3.15–3.30 (m, 1 H), 4.55–4.60 (dd, J = 11.9, 5.9 Hz, 1 H,
CHNH), 4.90 (m, 1 H, NH), 7.00–7.15 (m, 4 H, ArH), 7.35 (d,
J = 8.0 Hz, 2 H, ArH), 7.80 (d, J = 8.0 Hz, 2 H, ArH).
+
(m, 1 H, CHOH), 6.86 (m, 1 H, ArH), 7.21 (m, 1 H, ArH), 7.38 (m,
1
H, ArH).
MS (EI): m/z = 261 (M – 1)+.
MS (EI): m/z = 308 (M – N ) .
3
1
-Azido-3-(2-naphthyloxy)-2-propanol (Table 1, Entry 12)
1
N-[2-Azido-1-(4-chlorophenyl)ethyl]-4-methyl-1-benzene-
sulfonamide
IR (neat): 2100, 3280 cm .
Liquid.
–
1
–
1
IR (neat): 2100, 3385 cm .
1H NMR (200 MHz, CDCl3): = 2.50 (br s, 1 H, OH), 3.55 (t,
J = 4.6 Hz, 1 H, CHN ), 3.85 (t, J = 6.4 Hz, 1 H, CHN ), 4.10 (d,
J = 6.5 Hz, 2 H, OCH ), 4.15–4.27 (m, 1 H, CHOH), 7.05–7.15 (m,
1H NMR (200 MHz, CDCl3): = 2.40 (s, 3 H, ArCH ), 3.45–3.55
3
(
(
m, 2 H, CH N ), 4.40–4.50 (dd, J = 8.9, 5.1 Hz, 1 H, CHNH), 5.20
m, 1 H, NH), 7.10–7.20 (m, 4 H, ArH), 7.30 (d, J = 8.2 Hz, 2 H,
2 3
3
3
2
ArH), 7.75 (d, J = 8.1 Hz, 2 H, ArH).
2
H, ArH), 7.25–7.45 (m, 2 H, ArH), 7.65–7.80 (m, 3 H, ArH).
+
MS (EI): m/z = 242 (M – 1)+.
MS (EI): m/z = 308 (M – N ) .
3
1
N–(2-Azido-1-cyclohexylethyl)-4-methyl-1-benzenesulfona-
1
-Azido-3-[3-phenyl-(E)-2-propenyloxy]-2-propanol (Table 1,
mide (Table 2, Entry 4)
Liquid.
Entry 13)
Liquid.
–
1
–
1
IR (neat): 2100, 3380 cm .
IR (neat): 2100, 3390 cm .
1H NMR (200 MHz, CDCl3): = 0.60–1.80 (m, 1 H, cyclohexyl),
1H NMR (200 MHz, CDCl3): = 2.45 (br s, 1 H, OH), 3.39 (dd, 2
2
1
.40 (s, 3 H, CH ), 3.26 (dd, 1 H, J = 3.2, 9.4 Hz, CH N ), 3.30 (dd,
H, J = 2.9, 5.9 Hz, CH N ), 3.49–3.57 (m, 2 H, OCH ), 3.92–3.99
3
2
3
2
3
2
H, J = 3.2, 9.4 Hz, CH N ), 5.20 (m, 1 H, NH), 7.30 (d, J = 7.5 Hz,
(
(
m, 1 H, CHOH), 4.21 (dd, 2 H, J = 1.0, 6.1 Hz, OCH ), 6.20–6.30
m, 1 H, olefinic), 6.60 (d, 1 H, J = 15.9 Hz, olefinic), 7.22–7.42 (m,
2
3
2
ArH), 7.80 (d, J = 7.5 Hz, ArH).
5
H, ArH).
+
MS (EI): m/z = 101 (M – CH N ) .
2
3
MS (EI): m/z = 160 (M – 1)+.
N-(2-Azidocyclohexyl)-4-methylbenzenesulfonamide (Table 2,
Entry 5)
Liquid.
IR (neat): 2100, 3320 cm–1.
1
(
N-(2-Azido-2-phenyethyl)-4-methyl-1-benzenesulfonamide
Table 2, Entry 1)
Liquid.
–
1
IR (neat): 2100, 3270 cm .
1H NMR (200 MHz, CDCl3): = 2.45 (s, 3 H, ArCH ), 2.95–3.10
1
H NMR (400 MHz, CDCl ): = 1.20–1.40 (m, 4 H), 1.60–1.75 (m,
3
2 H), 2.00–2.15 (m, 2 H), 2.45 (s, 3 H, ArCH ), 2.85–2.95 (m, 1 H,
3
3
CHN ), 3.00–3.10 (m, 1 H, CHNH), 4.80 (d, J = 5.4 Hz, 1 H, NH),
(m, 1 H, CHNH), 3.10–3.30 (m, 1 H, CHNH), 4.55–4.65 (dd,
3
7
.30 (d, J = 8.1 Hz, 2 H, ArH), 7.80 (d, J = 8.1 Hz, 2 H, ArH).
J = 7.7, 5.0 Hz, 1 H, CHN ), 5.30–5.50 (m, 1 H, NH), 7.05–7.40 (m,
3
7
H, ArH), 7.75 (d, J = 8.0 Hz, 2 H, ArH).
MS (EI): m/z = 294 (M+).
+
MS (EI): m/z = 274 (M – N ) .
3
N-(2-Azidocyclopentyl)-4-methylbenzenesulfonamide (Table 2,
Entry 6)
Liquid.
1
N-(2-Azido-1-phenylethyl)-4-methyl-1-benzenesulfonamide
1
H NMR (200 MHz, CDCl3): = 2.40 (s, 3 H, ArCH ), 3.35–3.55
3
(
d, J = 5.6 Hz, 2 H, CH N ), 4.70–4.85 (dd, J = 11.8, 5.5 Hz, 1 H,
IR (neat): 2105, 3270 cm–1.
2
3
CHNH), 5.65–5.75 (m, 1 H, NH), 7.10–7.40 (m, 7 H, ArH), 7.60 (d,
J = 8.0 Hz, 2 H, ArH).
1
H NMR (400 MHz, CDCl ): = 1.30–1.50 (m, 1 H), 1.60–1.75 (m,
3
3
H), 1.95–2.10 (m, 2 H), 2.45 (s, 3 H, ArCH ), 3.30–3.50 (m, 1 H,
3
Synthesis 2002, No. 15, 2254–2258 ISSN 0039-7881 © Thieme Stuttgart · New York

2
258
G. Sabitha et al.
PAPER
CHN ), 3.60–3.70 (m, 1 H, CHNH), 4.85 (d, J = 6.5 Hz, 1 H, NH), References
3
7
.30 (d, J = 8.0 Hz, 2 H, ArH), 7.80 (d, J = 8.0 Hz, 2 H, ArH).
(
(
(
1) IICT communication No. 03/02/02.
2) Parker, R. E.; Isaacs, N. S. Chem. Rev. 1959, 59, 737.
3) (a) Osborn, H. M. I.; Sweeney, J. Tetrahedron: Asymmetry
MS (EI): m/z = 281 (MH+).
N-(2-Azidocyclooctyl)-4-methylbenzenesulfonamide (Table 2,
Entry 7)
Liquid.
1997, 8, 1693. (b) Coleman, R. S. Synlett 1998, 1031.
(
4) (a) Erden, I. In Comprehensive Heterocyclic Chemistry,
Vol. IA; Padwa, A., Ed.; Pergamon Press: Oxford, 1996,
Chap. 1.03. (b) Bartok, M.; Lang, K. L. In Chemistry of
Heterocyclic Compounds, Vol. 42; Weissberger, A.; Taylor,
E. C., Eds.; Wiley: NewYork, 1985, Part 3, 1.
–
1
IR (neat): 2100, 3275 cm .
1
H NMR (400 MHz, CDCl ): = 1.10–1.50 (m, 8 H), 1.60–1.80 (m,
3
2
H), 1.93–2.20 (m, 2 H), 2.40 (s, 3 H, ArCH ), 2.90–3.00 (m, 1 H,
3
(
5) For Reviews on aziridine chemistry, see: (a) Tanner, D.
Angew. Chem., Int. Ed. Engl. 1994, 33, 599. (b) Padwa, A.;
Woolhouse, A. D. In Comprehensive Heterocyclic
CHN ), 3.05–3.10 (m, 1 H, CHNH), 4.85 (d, J = 5.8 Hz, 1 H, NH),
7
MS (EI): m/z = 323 (MH+).
3
.30 (d, J = 8.0 Hz, 2 H, ArH), 7.70 (d, J = 8.0 Hz, 2 H, ArH).
Chemistry, Vol. 7; lwowski, W., Ed.; Pergamon: Oxford,
1
(
1
984, 47–93. (c) Kasai, M.; Kono, M. Synlett 1992, 778.
d) Osborn, H. M. I.; Sweeney, J. Tetrahedron: Asymmetry
997, 8, 1693. (e) Rayner, C. M. Synlett 1997, 11.
1
(
N-(2-Azidomethylpentyl)-4-methyl-1-benzenesulfonamide
Table 1, Entry 8)
Liquid.
(
(
6) The Chemistry of the Azido Group; Patai, S., Ed.; Wiley:
New York, 1971.
7) Chandrasekhar, M.; Sekar, G.; Singh, V. K. Tetrahedron
Lett. 2000, 41, 10079.
8) Bergmeir, S. C. Tetrahedron 2000, 56, 2561.
9) (a) Rogers, G. A.; Parsons, S. M.; Nilsson, D. C.; Bahr, L.
M.; Kornreich, W. D.; Kaufman, R.; Jacobs, R. S.; Kirtman,
B. J. Med. Chem. 1989, 32, 1217. (b) Chng, B. L.; Ganesan,
A. Bioorg. Med. Chem. Lett. 1997, 7, 1511.
–
1
IR (neat): 2095, 3380 cm .
1H NMR (200 MHz, CDCl3): = 0.80 (t, J = 7.0 Hz, 3 H, CH3),
1
ArCH ), 3.25–3.40 (m, 3 H, CHN , CH NH), 4.60 (d, 1 H, J = 7.5
Hz, NH), 7.35 (d, J = 8.2 Hz, 2 H, ArH), 7.75 (d, J = 8.4 Hz, 2 H,
ArH).
.10–1.30 (m, 4 H, CH ), 1.35–1.50 (m, 2 H, CH ), 2.50 (s, 3 H,
2
2
(
(
3
3
2
+
MS (EI): m/z = 240 (M – CH N ) .
2
3
(
10) Scriven, E. F. V.; Turnbull, K. Chem. Rev. 1988, 88, 297.
N-(2-Azidooctyl-4-methylbenzenesulfonamide) (Table 2, Entry
(11) (a) Coe, D. M.; Myers, P. L.; Parry, D. M.; Roberts, S. M.;
Storer, R. J. Chem. Soc., Chem. Commun. 1990, 151.
(b) Jacobs, G. A.; Tino, J. A.; Zahler, R. Tetrahedron Lett.
1989, 30, 6955.
9
)
Liquid.
–
1
IR (neat): 2105, 3280 cm .
(
12) Hou, J. W.; Dai, L.-X. J. Org. Chem. 2000, 65, 1344.
1
H NMR (200 MHz, CDCl ): = 0.85 (t, J = 7.1, Hz, 3 H, CH3),
3
(13) (a) Crotti, P.; Di Bussolo, V.; Favero, L.; Macchia, F.;
Pineschi, M. Eur. J. Org. Chem. 1998, 5, 1675. (b) Blandy,
C.; Choukroun, R.; Gervais, D. Tetrahedron Lett. 1983, 24,
1
.00–1.35 (m, 7 H, CH ), 1.35–1.60 (m, 3 H, CH ), 2.40 (s, 3 H,
2
2
ArCH ), 3.20–3.40 (m, 3 H, CHN , CH NH), 4.65 (d, 1 H, J = 7.7
3
3
2
Hz, NH), 7.35 (d, J = 7.9 Hz, 2 H, ArH), 7.80 (d, J = 8.1 Hz, 2 H,
ArH).
4189. (c) Nugent, W. A. J. Am. Chem. Soc. 1992, 114, 2768.
(d) For a recent review, see: Paterson, I.; Berrisford, D. J. In
+
Organic Synthesis Highlights, Vol. III; Mulzer, J.;
Waldmann, H., Eds.; Wily-VCH: Weinheim, 1998.
MS (EI): m/z = 268 (M – CH N ) .
2
3
(
(
e) Muller, E. P. Helv. Chim. Acta 1882, 65, 1617.
f) Schneider, C. Synlett 2000, 12, 1840. (g) Li, Z.;
1
(
N-(1-Azidomethylnonyl)-4-methyl-1-benzenesulfonamide
Table 2, Entry 10)
Liquid.
Fernandez, M.; Jacobsen, E. N. Org. Lett. 1999, 1, 1611.
(
14) Onaka, M.; Sugita, K.; Izumi, Y. J. Org. Chem. 1989, 54,
–
1
IR (neat): 2100, 3390 cm .
1
116.
1
H NMR (200 MHz, CDCl ): = 0.85 (t, J = 7.2, Hz, 3 H, CH3),
(15) (a) Saito, S.; Nishikawa, T.; Yokoyama, Y.; Yamashita, S.
Tetrahedron Lett. 1989, 30, 4153. (b) Saito, S.; Nishikawa,
T.; Yokoyama, Y.; Mariwake, T. Tetrahedron Lett. 1990,
31, 221.
3
1
.05–1.30 (m, 6 H, CH ), 1.32–1.60 (m, 2 H, CH ), 2.45 (s, 3 H,
2
2
ArCH ), 3.20–3.40 (m, 3 H, CHN , CH NH), 4.95 (d, 1 H, J = 7.6
Hz, NH), 7.30 (d, J = 8.5 Hz, 2 H, ArH), 7.80 (d, J = 8.6 Hz, 2 H,
3
3
2
ArH).
(16) Tamami, B.; Mahdev, H. Tetrahedron Lett. 2001, 42, 8721.
(17) Leung, W.-H.; Yu, M.-T.; Wu, M.-C.; Yeung, L.-L.
Tetrahedron Lett. 1996, 37, 891.
+
MS (EI): m/z = 296 (M – CH N ) .
2
3
(
(
(
(
(
18) Ferraris, D.; Drury, W. J. III; Cox, C.; Lectka, T. J. Org.
Chem. 1998, 63, 4568.
19) Sabitha, G.; Babu, R. S.; Rajkumar, M.; Reddy, C. S.;
Yadav, J. S. Tetrahedron Lett. 2001, 42, 3955.
20) Sabitha, G.; Satheesh Babu, R.; Shashikumar, M; Yadav, J.
S. New. J. Chem., 2002, in press.
Acknowledgments
RSB and MSKR thank CSIR New Delhi for the award of fel-
lowships.
21) Sabitha, G.; Syamala, M.; Yadav, J. S. Org. Lett. 1999, 1,
1701.
22) Sabitha, G.; Babu, R. S.; Rajkumar, M.; Yadav, J. S. Org.
Lett. 2002, 4, 343; and references cited therein.
Synthesis 2002, No. 15, 2254–2258 ISSN 0039-7881 © Thieme Stuttgart · New York