indi an Journ al of Chemistry
Vol. 438, September 2004, pp. 2024-2026
Note
Iodoazidation of olefins by polymer-bound
iodate (I) reagents
Md Abu! Hashem*, & Tahmina Haque
Department of Chemistry, Jahang irnaga r University,
Savar, Dhaka- 1342, Bangladesh
E-mail: chem @ juni v.ed u
Received II JL;ly 2003; accepted (revised) 28 October 2003
So me new exa mpl es of iodoazidation of o le fin s by polymerbo und iodoazide 1 are descri bed. In th e case of dienes, good
yie lds of mono-adduets are obtained when small equivalent of
polymer-bound reagen t is used.
IPC: Int.CI. 7 C 07 C 11/00
Nowadays, solid phase synthesis of the polymerbound iodoazides has attracted great attention t -J.
Recently, Kirschning and co-workers4 demonstrated
that functionalized polymers like the novel
electrophilic polystyrene-supported iodoazide 1,
.[ ~ NMe
3
r( N
3
hJ
is stable, non-explo-
sive and synthetically behaves like iod ine azide (IN 3)
which could effectively be utilized in the synthesis of
the polymer-bound iodoazides with mmtmum
purification . We have made use of the res in 1 to carry
out iodoazidation of olefins 2-7 and obtained I, 2azido-iodo anti addition products in high yields
(Table 1).
Except for the a-terpineol 5 iodoazi des 2a,b, 3a,
4a, 6a and 7a,b are obtained in good to excellent
yield. They are conveniently purified by filtration and
removal of the so lven t. lodoazidatio n of 1-octene 2
using Kirschning's procedure 1 resulted in a mixture
of two isomeric compounds, 2-azido-1-iodooctane 2a
and 1-azido-2-iodooctane 2b in 3:1 ratio (Tables I
and II) .
Cyclic olefins like 1-methyl-1-cyclohexene 3 and
4-methyl-1-cyclohexene 4 gave only one product each
(3a and 4a respectively) in which, surp ri singly, th e
azide function is at ]-position . Iodoazidation of a terpineol 5 yielded Sa (Table I) in which again the
azido group occupies the sterically unfavourabl e !position ( 13 C NMR, Table II).
Table I - lodoazi dat ion of olefins and dienes by the pol y mer- supported iodoazide 1
t, n (1)
[ equiv]
Olefin
Product
Ratio
HA
HA
I
I
4 hr, 5 H 3C-(CH 2 )5 CH-C-ll-1 3C-(CH 2 )5 CH-C-N 3
I I
I I
N 3 BH 3
2
2a
6
6 hr, 5
I
3:1
92 %
BH 3
2b
I Me
r"+'N
4~
5
Yield
%
3
3 2 I
90%
3a
M~
4
5 hr, 5
s~·~'N3
Me~
I
3
88%
4a
-Contd
NOTES
2025
Table I - lodoazidation of olefi ns and dienes by the polymer-supported iodoazide 1-Contd
I
7 hr, 3.5
46 %
3
0
5 hr, 3.5
:at
6 5
6
92%
I
6a
k}-I3
1
A
7 hr, 3.5
7
2LL+-UI
7a
8 7
10
3n~l
2~~
8 7 N3
3:2
93%
7b
Table II - Spectral data of the products
Compd
IR (cm-1)
2a
2108 (-N=N-str.)
2988,2890(C-H
str.), 1466, 1377 (CH def.)
PMR (8)
3.39 (ddt, IH , CH-N 3), 3.3 (dd, IH, CHA1), 3.26 (dd, I H, CH 8 -l), 1.57-1.69 (m,
2H), 1.31-1.42 (m, 8H), 0.90 (t, 3H, CH 3)
13
C NMR(8)
13
C- DEPT NMR(8)
62.7(CH-N 3),34.4(C-3),
31.5(C-4), 28.8(C-5),
25.7 (C-6), 22.5 (C-7),
14.0 (CH 3), 8.5 (CHrl)
Upside signals: 62.7 (CH-N 3) ,
14.0 (CH 3) Downside signals:
34.4 (C-3), 31.5 (C-4), 28.8
(C-5), 25.7 (C-6), 22.5 (C-7),
8.5 (CH2-I)
2b
2108 (-N=N-str.)
2988,2890(C-H
str.), 1466, 1377 (CH def.)
4.10 (ddt, IH, CH-I), 3.75 (dd,IH, CHANJ), 3.65 (dd, I H, CH 8 -N 3), 1.57-1.69
(m, 2H), 1.30-1.42 (m, 8H), 0.89 (t, 3H,
CH 3)
59.0 (CH 2-N 3), 37.2 (C3), 32.3 (CH-I), 29.7 (C4), 28.4 (C-5), 25 .7 (C6), 22.5 (C-7), 14.0
(CH 3)
Upside signals: 32.3 (CH-I),
14.0 (CH 3) . Downside
signals: 59.0 (CHrN 3) 37.2
(C-3), 29.7 (C-4), 28 .4 (C-5),
25 .7 (C-6), 22.5 (C-7)
3a
2089 (-N=N-str.)
2939,2860(C-H
str.), 1444, 1383 (CH def.)
4.24 (dd, IH, 1=3.95 Hz, CH-I), 2.28 (dt,
I H, 6-H), 1.97-2.06 (m, 2H, 3-H), 1.691.74 (m,IH, 6-H), 1.61-1.67 (m, 2H, 5H),
1.36-1.53 (m,2H,4-H),
1.47(s,
3H,CHrC-NJ)
63.9(C-N 3 ) , 41.2 (CH 3),
35.9(C-6), 35.3 (C-3),
26.2 (C-5), 22.1 (C-4 ),
23.5 (CH-I)
Upside signals: 41.2 (CH 3),
23.5 (CH-I) Downside
signals: 35.9 (C-6), 35 .3 (C3), 26.2 (C-5), 22.1 (C-4) (No
C-N 3 signal is present in the
DEPT program)
4a
2089
(-N=N-str.)
2936, 2890 (C-H
str.), 1441, 1385 (CH def.)
63.8 (CH- N3), 34.6 (C6), 31.4 (C-3), 30.9
(CH-I), 29.2 (C-5), 26.9
(C-4), 20.5 (CH 3)
Upside signals: 63.8 (CH-N 3),
30.9 (CH-I), 26.9 (C-4), 20.5
(CH 3 ) Downside signals: 34.6
(C-6), 31.4 (C-3), 29.2 (C-5)
Sa
2100 (-N=N-str.)
3588 (0-H str.),
1169, 1400 (C-0
str.), 2968, 2896 (CH str.), 1458, 1437
(C-H def.)
4.37 (ddd, IH, CH-I), 3.93 (ddd, IH, CHN3), 2.18-2.45(m,l H,6-H), 1.88-2.0 (m,
2H, 3-H), 1.66-1.76 (m, 2H, 6-H and 5H), 1.54-1.57 (m, I H, 5-H), 1.35-1.4 (m,
IH, 4-H), 0.96 (d, 3H, CH 3)
4.47 (dd, IH, CH-I), 1.97-2.03 (m, IH, 6H), 1.92-1.97 (m, IH, 3-H), 1.85-1.90 (m,
IH, 3-H), 1.77-1.83 (m,IH,6-H), 1.601.65(m,2H,5-H), 1.58 (s,l H,-OH), 1.52
(s,3H, CH 3), 1.35-1.45 (m, I H, 4-H), 1.16
(s, 3H CH 3), 1.15 (s, 3H, CH 3)
63.3 (C-N 3), 69.7 (COH), 43.5 (C-4), 40.4
(CH 3), 33.7 (C-6), 32.0
(C-3), 29.0(CH-I), 27.5
(CH 3), 27.2 (CH 3), 22.3
(C-5)
Upside signals: 43.5 (C-4),
40.4 (CH 3), 29.0 (CH-I), 27.5
(CH 3), 27.2 (CH 3). (C-1 and
C-1 0 being tertiary carbons
are absent). Downside
signals: 33.7(C-6), 32.0 (C3), 22.3 (C-5)
- Contd
INDIAN J. C H EM ., SEC 8 , SEPTEMB ER 2004
2026
Table I I - Spec tral data o f the products-
Comd
Compd
IR (c m-1)
PMR (o)
6a
2 106 (-N=N -str.)
165 5 (C=C str. )
2896, 2855 (C- H
str. ), 1458, 136 1 (C H deL)
5.67-5.69 (m, I H , 2-H ), 5.47-5.49 (m, I I-1 ,
1-H), 4.22 (cldd, I I-1 , C H-I ), 3.80 (ddcl,
I I-1 , C H -N 3), 2.92-2.97 (m.l H ,3- H),2 .72 2.78( m, I H,6- H), 2.64-2 .70 (m. I H, 3- I-1 ),
2.2 1-2.28 (m. I I-1 ,6- I-1 )
124.9(C-2), 123.3(C- I ),
63.0 (C I-1 - N 3), 27. 1
(C I-1 -1), 35.5 (C-3), 30.0
(C-6)
Upside signals: 124.9 (C-2),
123.3 (C- 1), 63 .0(C H - N 3),
27. 1(C I-I -I) Downside signals :
35.5 (C-3 ), 30 .0 (C-6)
7a
2 106 (- N=N-str. )
1655(C=C str. )
5.53 (dd, I H,2- H), 5.6 (dd , I I-1 , 3-I-1 ) 4.22
(dd, I H ,C I-I -N 3), 3.39( ddd, I I-1 , C I-1-1 ),
3. 13-3. 15(m, 11-1 ,5- 1-1 ),2 .60-2.66
( 111 , I I-1 , 8- I-1 ), 2.47- 2. 51 ( 111 , I I-1 ,8- I-1 ).
2.25-2 .30 ( m, 2H , I 0- I-1 ), 2. 12- 2.1 7( 111,
I I-1 ,4- H), 2.0 (dd, I I-1 , 1- I-1 ), 1.46- 1.53
(m, I H, 9- I-1 )
132.0(C-3), 13 1.3(C-2),
64.0(C H .. N 3),53.8(C-5),
5 1. 1 (C-4), 46.6 (C- 1),
42.7 (C -9), 36.5 (C-8),
32. 1 (C- 10) , 3 1.7(C H -I)
Upside signa ls: 132.0 (C-3).
13 1.3 (C-2), 64.0 (C I-I -N 3),
53.8 (C-5), 5 1. 1 (C-4), 46.6
(C-1 ), 42.7 (C-9), 31.7 (CHI). Downside signals: 36.5(C·
8), 32 .1 (C- 10)
7b
2 106 ( -N=N-str. )
1655 (C=C str. )
5.68(dd, I I-1 , 3- I-1 ), 5.70 (dd, I I-1 , 2- I-1 ),
4.40(d d, I I-1 , C I-1-1 ), 3. 25 (d dd , I I-I ,C I-I N 3) , 3.02-3.03(111 , I I-1 , 8- H) 2.60-2.66 (m ,
Il-l , 5- 1-1) 2.47-2 .50 (111 , I H,8- I-1 ),2.202.25(m,2 I-I , I 0- I-1 ) 2. 12-2. 17 (111 , I I-1 ,4- H),
2 O(clcl, I 1-1, 1- I-1 ), 1.46 - 1.53( 111, I I-1 ,9- H)
132.0 (C-2), 13 1.0 (C3), 6 1. 1 (C H -N 3), 53.2
(C- 5), 51.9 (C-4), 48 .0
(C- 1), 41.0 (C-9), 37 .3
(C-8) , 36.4 (C l-1 -1),
3 1.8(C- 10)
Upside signals: 132.0 (C -2),
131.0 (C-3). 6 1.1 (C I-1 - 3) ,
53.2 (C-5), 51.9 (C-4). 48.0
(C- 1), 4 1.0(C-9), 36.4 (CI-1- 1)
Downside signals: 3 1.8 (C10), 37.3 (C-8)
lodoaz idation o f th e conju gated di e ne 6 res ulted
in 4-az ido-5-iodo-l-cyc lohex e ne 6a w hereas the
no n-co nju gated di e ne, dicyclope ntadi e ne 7 yi e lded
two isomeric products, 6 -az id o-7 -iodote tracycl o9
[5 .2 . I .0 5 ]decene-2 7a and 7-az id o-6-i odote tracyc lof5.2 .1.059]dece ne-2 7b 111 3 :2 rat io ( 11-l NMR,
Table II).
Experimental Procedure
Infrared s pec tra were recorded o n a SHIMADZU
Fr!R DR-800 l spectrome te r. Th e s pectra were
1
reco rded e ith er as thin film o r KBr di sk. H NMR
spec tra were recorded in CDCI 3 usin g a Bruker WH
400 MH z spectro meter with TMS as inte rn al
sta nd ard . The che mi ca l shifts were ex pressed in 813
va lu es. C NMR spectra we re reco rded o n a Bruke r
WH 400 MH z spectro meter w ith D EPT prog ram.
13
C N MR(o)
11
C- DE PT N MR (o)
These spectra were a lso reco rded in CDC I3 us in g
TMS as interna l standa rd . Co lumn chro matog raphy
was carri ed ou t in s ili ca gel (23 0-400 mes h).
Acknowledgement
Authors th a nk the B ang lades h Co unci l of Sc ienti fic
a nd Indu strial Resea rch (B CSIR ) Laboratori es fo r a ll
NMR meas ure me nts a nd Mini stry of Sc ie nce and
T echn o logy, Bang ladesh fo r finan c ia l sup po rt.
References
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2
3
4
5
Kirschni ng A, Plumeier C & Rose L, Chen / Con11111111 , 1998,
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Has hem A, Jung A, Ri es M & Kirschni ng A, Synlet , 1998, 196.
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