Bromination of organic allylic compounds by using N,N′-dibromo-N,N′-1,2-ethane diyl bis(2,5-dimethyl benzene sulphonyl)amine

Article abstract of DOI:10.1081/SCC-120005417

N,N′-Dibromo-N,N′-1,2-ethane diyl bis(2,5-dimethyl benzene sulphonyl)amine is an efficient brominating agent for bromination of allylic positions of different organic compounds. This reagent in presence of benzoyl peroxide can brominates the allylic positions of organic compounds in ambient conditions in carbon tetrachloride.

Full text of DOI:10.1081/SCC-120005417

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BROMINATION OF ORGANIC ALLYLIC COMPOUNDS BY
USING N,N′-DIBROMO-N,N′-1,2-ETHANE DIYL BIS(2,5-
DIMETHYL BENZENE SULPHONYL)AMINE
Ardeshir Khazaei a , Ramin Ghorbani Vaghei a & Ebrahim Karkhanei a
a Department of Chemistry , Faculty of Science , Bu-Ali Sina University , Hamadan, Iran
Published online: 18 Oct 2011.
To cite this article: Ardeshir Khazaei , Ramin Ghorbani Vaghei & Ebrahim Karkhanei (2002) BROMINATION OF ORGANIC ALLYLIC
COMPOUNDS BY USING N,N′-DIBROMO-N,N′-1,2-ETHANE DIYL BIS(2,5-DIMETHYL BENZENE SULPHONYL)AMINE, Synthetic
Communications: An International Journal for Rapid Communication of Synthetic Organic Chemistry, 32:14, 2107-2113, DOI:
10.1081/SCC-120005417
To link to this article: http://dx.doi.org/10.1081/SCC-120005417
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SYNTHETIC COMMUNICATIONS
Vol. 32, No. 14, pp. 2107–2113, 2002
BROMINATION OF ORGANIC
ALLYLIC COMPOUNDS BY USING
N,N0-DIBROMO-N,N0-1,2-ETHANE DIYL
BIS(2,5-DIMETHYL BENZENE
SULPHONYL)AMINE
*
Ardeshir Khazaei, Ramin Ghorbani Vaghei,
and Ebrahim Karkhanei
Department of Chemistry, Faculty of Science,
Bu-Ali Sina University, Hamadan, Iran
ABSTRACT
N,N0-Dibromo-N,N0-1,2-ethane diyl bis(2,5-dimethyl benzene
sulphonyl)amine is an efficient brominating agent for bromi-
nation of allylic positions of different organic compounds.
This reagent in presence of benzoyl peroxide can brominates
the allylic positions of organic compounds in ambient
conditions in carbon tetrachloride.
Selective bromination of allylic compounds in organic chemistry is
very important and can be achieved by many reagents.[1] One of the classic
reagents is N-bromosuccinimide which is used for bromination of allylic
positions.[2,3] Reaction mechanism is shown by McCoy and Douben,[4]
*Corresponding author. E-mail: khazaei_1326@yahoo.com
2107
DOI: 10.1081/SCC-120005417
Copyright & 2002 by Marcel Dekker, Inc.
0039-7911 (Print); 1532-2432 (Online)
www.dekker.com

2108
KHAZAEI, VAGHEI, AND KARKHANEI
and further reaction mechanism is shown that a trace of bromine molecule is
present with NBS.[5]
In these procedures, the bromination of allylic positions were not
occurred without using of peroxide and also the yield of bromination
product were not excellent.
For this reason we attempted to work with our previous reagent to
compare the ability of it with NBS[6] (Scheme 1).
Scheme 1.
Here, we report a simple procedure for the bromination of allylic
positions of different types of alkenes (Scheme 2). Bromination can be read-
ily carried out by placing of II, alkene (1) in CCl4 as the solvent in a reaction
vessel and stirring the resulting mixture for 1–1.5 h under reflux conditions.
The brominated alkenes were obtained by filtration and evaporation of the
solvent. The results are shown in the Table1.
Scheme 2.
In order to show the capability of our reagent, the results are
compared with NBS (Table 2).
The advantages of N-bromosulfonamide (II) are as follows:
1. The preparation of N-bromosulfonamide is very easy.
2. N-bromosulfonamide is stable for time in atmospheric condition.
3. After reaction of N-bromosulfonamide with substrate, the sulfon-
amide is recovered and can be reused many times without
decreasing the yield.

BROMINATION OF ORGANIC ALLYLIC COMPOUNDS
2109

2110
KHAZAEI, VAGHEI, AND KARKHANEI
Table 2. Comparison of the Results Obtained by Our Method
with Those Reported by NBS
Yields
Substrate
II
NBS
Cyclohexene
Methyl but-2-enolate
2-Heptene
4-Methyl ethyl pant-2-enolate
2-Methyl methyl but-2-enolate
60
88
73
82
45[7]
86[7]
58–64[8]
81[9]
[10]
5145
EXPERIMENTAL SECTION
IR and NMR spectra were recorded using a Shimadzu 435-U-04 spec-
trophotometer (KBr pellets) and a 90 MHz Geol FT-NMR spectrometer,
respectively. NMR chemical shifts were measured relative to TMS (int; 1H).
Reagent was prepared by our previously reported procedure.[6]
Bromination of Cyclohexene with N,N0-Dibromo-N,N0-1,2-ethylene
bis(2,5-Dimethyl Benzenesulfonamide). A Typical Procedure
In a 50 mL round-bottomed flask 5.41g (0.0098 mol) of N-bromo-
sulfonamide, 30 mL of carbon tetrachloride, 1.61 g (0.0196 mol) of redis-
tilled cyclohexene and 0.05 g of benzoyl peroxide is placed. The flask is
equipped with a condenser and the reaction mixture allowed to stand at
room temperature. After a short induction period the reaction mixture
becomes warm and light, colourless sulfonamide(crystals) begin to preci-
pitate. The flask was cold in ice-water. After the reaction the sulfonamide
was filtered under suction and washed with 10 mL of cold carbon tetra-
chloride. Distil the filterate on a boiling water bath, first of all the carbon
tetrachloride was removed (b.p. 77ꢀC), then, unreacted cyclohexene (b.p.
83ꢀC). The residue was distilled (b.p. 66–67ꢀC/20 mm) with 60% yield.
This compound was identified by T.L.C, IR, NMR spectroscopies and
elemental analysis. IR (KBr pellets) 3050, 2950, 1650, 1170, 650 cmÀ1
;
1H-NMR (CDCl3): ꢀ ¼ 5.634 (s, 2H), ꢀ ¼ 3.415 (q. 1H), ꢀ ¼ 1.996
(brd, 2H), ꢀ ¼ 1.196 (t, 2H), 13C-NMR : ꢀ ¼ 11.426, 14.340, 16.886, 30.018,
120.878, 127.204. Found: C, 54.73; H, 6.90%. Calcd. for C6H9 Br: C, 54.92;
H, 6.92%.

BROMINATION OF ORGANIC ALLYLIC COMPOUNDS
3,7-Dibromo-1,5-cyclooctadiene
2111
The residue was distilled (b.p. 134–136ꢀC/20 mm) with 65% yield. This
compound was identified by T.L.C, IR, NMR spectroscopies and elemental
;
analysis. IR (KBr pellets) 3100, 2970, 1690, 1200, 645 cmÀ1 1H-NMR
(CDCl3): ꢀ ¼ 5.624 (brd, 4H), ꢀ ¼ 3.419 (q, 2H), ꢀ ¼ 1.197 (t, 4H),
13C-NMR: ꢀ ¼ 15.266, 30.286, 122.657, 128.119. Found: C, 36.22; H, 3.55%.
Calcd. for C8H10Br2: C, 36.12; H, 3.80%.
Methyl 4-Bromobut-2-enoate
The residue was distilled (b.p. 77–78ꢀC/8 mm) with 87% yield. This
compound was identified by T.L.C, IR, NMR spectroscopies and elemental
;
analysis. IR (KBr pellets) 3050, 2950, 1720, 1450, 1220 cmÀ1 1H-NMR
(CDCl3): ꢀ ¼ 3.8 (s, 3H), ꢀ ¼ 4.1(d, 2H), ꢀ ¼ 6 (d, 1H), ꢀ ¼ 7 (shul., 1H),
13C-NMR: ꢀ ¼ 165.341, 127.482, 120.542, 65.324, 31.15. Found: C, 33.62, H,
3.81%. Calcd. for C5H7BrO2: C, 33.54; H, 3.94%.
Ethyl 4-Bromobut-2-enoate
The residue was distilled (b.p. 94–95ꢀC/12 mm) with 89% yield. This
compound was identified by T.L.C, IR, NMR spectroscopies and elemen-
tal analysis. IR (KBr pellets) 3050, 2950, 1750, 1430, 1280, 1100, 1000,
1
900, 850 cmÀ1; H-NMR (CDCl3): ꢀ ¼ 1.3 (t, 3H), ꢀ ¼ 4.1(m, 4H), ꢀ ¼ 6 (d,
1H), ꢀ ¼ 7 (m, 1H); 13C-NMR: ꢀ ¼ 164.351, 128.483, 119.315, 64.232,
30.16. Found: C, 31.21; H, 4.61%. Calcd. for C6H9BrO2: C, 31.11;
H, 4.70%.
4-Bromo-2-heptene
The residue was distilled (b.p. 70–71ꢀC/32 mm) with 73% yield. This
compound was identified by T.L.C, IR, NMR spectroscopies and elemental
1
analysis. IR (KBr pellets) 3050, 2970, 1425, 670 cmÀ1; H-NMR (CDCl3):
ꢀ ¼ 1.3 (d, 3H), ꢀ ¼ 1.2 (m, 7H), ꢀ ¼ 4.1(m, 2H), ꢀ ¼ 6.1(m, 1H), ꢀ ¼ 7.2
(m, 1H); 13C-NMR: ꢀ ¼ 125.419, 121.316, 60.182, 31.513. Found: C, 42.21;
H, 7.92%. Calcd. for C7H14Br: C, 47.10; H, 7.81%.

2112
KHAZAEI, VAGHEI, AND KARKHANEI
3-Bromo-1-phenyl-1-propene
The residue (m.p. 27–29ꢀC) with 76% yield. This compound was
identified by T.L.C, IR, NMR spectroscopies and elemental analysis.
1
IR (KBr pellets) 3040, 2980, 1440, 680 cmÀ1; H-NMR (CDCl3): ꢀ ¼ 7.9
(d, 3H), ꢀ ¼ 7.1(d, 2H), ꢀ ¼ 8 (d, 1H), ꢀ ¼ 6.5 (t, 1H), ꢀ¼3.8 (d, 2H);
13C-NMR: ꢀ ¼ 125.310, 121.140, 62.650. Found: C, 51.92; H, 4.90%.
Calcd for C9H9Br: C, 51.90; H, 4.95%.
2-(Bromomethyl)acrylic Acid
The residue (m.p. 70–73ꢀC) with 74% yield. This compound was iden-
tified by T.L.C, IR, NMR spectroscopies and elemental analysis. IR (KBr
1
pellets) 3046, 2980, 1420, 670 cmÀ1; H-NMR (CDCl3): ꢀ ¼ 1.3 (m, 7H),
ꢀ ¼ 4 (m, 2H), ꢀ ¼ 6.2 (m, 1H), ꢀ ¼ 7.1(m, 2H); 13C-NMR: ꢀ ¼ 123.320,
120.432, 62.270, 30.151. Found: C, 43.92; H, 7.39%. Calcd. for C6H12Br:
C, 43.60; H, 7.42%.
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BROMINATION OF ORGANIC ALLYLIC COMPOUNDS
2113
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Received in the UK March 27, 2001