N,N′-dibromo-N,N′-1,2-ethanediylbis(benzene sulfonamide) as an efficient catalyst for acetylation and formylation of alcohols under mild conditions

Article abstract of DOI:10.1080/10426500902758337

An efficient method for the acylation and formylation of alcohols and phenols by using an acylating/formylating agent (acetic anhydride and formic acid) in the presence of a catalytic amount of N,N′-dibromo-N,N′-1, 2-ethanediylbis(benzene sulfonamide) under mild and solvent-free conditions at room temperature in good to excellent yields is described. The use of protic acids and metal Lewis acids is avoided.

Full text of DOI:10.1080/10426500902758337

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Phosphorus, Sulfur, and Silicon and the
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N,N′-Dibromo-N,N′–1,2-
ethanediylbis(benzene sulfonamide)
as an Efficient Catalyst for Acetylation
and Formylation of Alcohols Under Mild
Conditions
a
b
a
a
Ardeshir Khazaei , Amin Rostami , Zahra Rosta & Ali Alavi
a
Faculty of Chemistry, Bu-Ali Sina University, Hamadan, Iran
b
Department of Chemistry, Faculty of Science, University of
Kurdistan, Sanandaj, Iran
Published online: 28 Dec 2009.
To cite this article: Ardeshir Khazaei , Amin Rostami , Zahra Rosta & Ali Alavi (2009): N,N′-Dibromo-
N,N′–1,2-ethanediylbis(benzene sulfonamide) as an Efficient Catalyst for Acetylation and Formylation
of Alcohols Under Mild Conditions, Phosphorus, Sulfur, and Silicon and the Related Elements, 185:1,
181-186
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Phosphorus, Sulfur, and Silicon, 185:181–186, 2010
Copyright ꢀ
Taylor & Francis Group, LLC
C
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426500902758337
ꢀ
ꢀ
N,N -DIBROMO-N,N –1,2-ETHANEDIYLBIS(BENZENE
SULFONAMIDE) AS AN EFFICIENT CATALYST FOR
ACETYLATION AND FORMYLATION OF ALCOHOLS
UNDER MILD CONDITIONS
1
2
1
Ardeshir Khazaei, Amin Rostami, Zahra Rosta,
1
and Ali Alavi
1
Faculty of Chemistry, Bu-Ali Sina University, Hamadan, Iran
Department of Chemistry, Faculty of Science, University of Kurdistan,
Sanandaj, Iran
2
An efficient method for the acylation and formylation of alcohols and phenols by using
an acylating/formylating agent (acetic anhydride and formic acid) in the presence of a
ꢀ
ꢀ
catalytic amount of N,N -dibromo-N,N –1,2-ethanediylbis(benzene sulfonamide) under mild
and solvent-free conditions at room temperature in good to excellent yields is described. The
use of protic acids and metal Lewis acids is avoided.
ꢁ
ꢁ
Keywords Acetic anhydrides; acetylation; alcohols; N,N -dibromo-N,N -1,2-ethanediylbis
benzene sulfonamide); formic acid; formylation; phenols
(
INTRODUCTION
Among the various protecting groups used for the hydroxyl function, the acetyl is the
most common because of its ease of formation as well as mild conditions for deprotection.
O-Formylation is also a very important process, because the formate esters serve as a
1
useful synthetic reagent and intermediate. Due to the instability of the anhydride and the
acid chloride of formic acid, formylation of alcohols by formic acid and transesterfication
using ethyl formate are important synthetic reactions. Lewis acid catalysts have been used
to mediate the reaction between a hydroxyl group and acylating/formylating agent.2
Despite a number of methods that are currently available, new and efficient methods are
still in strong demand. On the other hand, these acetylation/formylation methodologies
suffer from disadvantages such as stringent and complicated conditions; use of hazardous,
strongly acidic, and costly materials; water-sensitive catalysts, etc.
–15
Received 5 September 2008; accepted 19 January 2009.
The authors acknowledge the Bu-Ali Sina University and Kurdistan University Research Councils for partial
support of this work.
Address correspondence to Ardeshir Khazaei, Faculty of Chemistry, Bu-Ali Sina University, Hamadan
6
5178-38683, Iran. E-mail: khazaei 1326@yahoo.com
1
81

1
82
A. KHAZAEI ET AL.
RESULTS AND DISCUSSION
Recently, we described the silylation of alcohols and phenols and tetrahydropy-
16
17
ꢁ
ꢁ
ranylation/depyranylation of hydroxy groups by N,N -dibromo-N,N –1,2-ethanediylbis
(
benzene sulfonamide) (BNBBS). In continuation of our studies in the applications of
18–20
N-halo reagents,
which are inexpensive, low in toxicity, highly stable towards hu-
midity, and air stable,21 we found that a catalytic amount of BNBBS is able to promote
quantitative acetylation and formylation of alcohols and phenols at room temperature, in
good to high yields, and requires only a short reaction time, in solvent-free conditions, with
a simple method and easy workup procedure (Scheme 1).
Scheme 1
Initially, BNBBS was prepared using the recently reported green method for preparation of
N-halosaccharin.22 In this method, the use or handling of the toxic and corrosive molecular
bromine and dichloromethane as solvent is avoided (Scheme 2). Also, the reaction condition
is mild, the yield is moderate, the isolation of the product in high purity is simple, and water
is the reaction solvent.
Scheme 2
The catalytic application of BNBBS was investigated for the acetylation of vari-
ous hydroxyl compounds using acetic anhydride under solvent-free conditions at room
temperature (Table I).
Subsequently, we discovered that the formylation of different types of alcohols can
be performed with formic acid in the presence of a catalytic amount of BNBBS under
solvent-free conditions at room temperature with good to high yields (Table II). Under
these reaction conditions, there were no side products.
The actual role of BNBBS is not clear. However, on the basis of the previously
reported mechanism,27 one explanation for this process is that BNBBS probably generates
small quantities of in situ HBr, which may be the actual catalyst for the acetylation and
formylation reactions (as a protic acid). Another explanation is that BNBBS might act as
+
a source for the formation of Br , which in turn activates the carbonyl group of Ac2O to
produce the highly reactive acylating agent (as a Lewis acid). However, at this time the

ACETYLATION AND FORMYLATION OF ALCOHOLS
183
Table I Acetylation of the alcohols or phenols (1 mmol) using Ac2O (1.5 mmol) catalyzed with BNBBS (0.1
mmol) under solvent-free conditions at room temperature
Producta
Yields (%)
b
[Ref]c
Entry
Substrate
Time (min)
1
2
3
4
4-OMe C6H4CH2OH
4-Cl C6H4CH2OH
4-NO2 C6H4CH2OH
60
60
120
120
4-OMe C6H4CH2OAc
4-Cl C6H4CH2OAc
4-NO2 C6H4CH2OAc
80
91
40
93
6, 10, 11, 5, 15, 2, 3
12, 5, 11,3
18, 12, 2,3
—
5
6
7
8
9
PhCH2CH2OH
PhCH(OH)Ph
CH3CH(Ph)OH
CH3(CH2)4CH(OH)CH3
300
360
180
15
PhCH2CH2OAc
PhCH(OAc)Ph
CH3CH(Ph)OAc
CH3(CH2)4CH(OAc)CH3
93
92
80
87
90
18, 10, 11, 4, 2, 3
21, 10, 4, 5,
10, 13, 5, 2,3, 4
18
10
8, 15, 11, 12, 2, 3, 4
1
1
0
1
20
20
94
95
18
8
1
1
2
3
360
20
50
88
5, 6, 12, 8, 7
15
a
1
All products were characterized by comparison of their spectral data ( H NMR, IR) with those of authentic
2
3–26
samples.
b
Isolated yields.
c
References for previously reported products.
precise role of BNBBS is not clear, and the actual role of this reagent should be studied in
further detail.
CONCLUSION
In summary, we have developed the catalytic application of BNBBS for acetylation
and formylation of hydroxyl compounds, essentially under neutral and solvent-free con-
ditions. In addition, the most notable advantages of this methodology are mild condition
(room temperature), low cost, easy preparation, low toxicity, easy workup, and high yield.
The use of protic acids and metal Lewis acids is avoided.

1
84
A. KHAZAEI ET AL.
Table II Formylation of alcohols using HCOOH (20 mmol) in the presence of a catalytic amount of BNBBS
0.1 mmol) at room temperature
(
Producta
Yields (%)
b
[Ref]c
Entry
Substrate
Time (min)
1
2
3
4
4-OMe C6H4CH2OH
4-Cl C6H4CH2OH
4-NO2 C6H4CH2OH
3
60
240
4-OMe C6H4CH2OCHO
4-Cl C6H4CH2OCHO
4-NO2 C6H4CH2OCHO
88
94
70
95
7,3, 4
9,13,2,3,4
4, 13,2,3
—
immediate
5
6
7
8
9
PhCH2CH2OH
PhCH(OH)Ph
CH3CH(Ph)OH
CH3(CH2)4CH(OH)CH3
40
60
90
45
80
PhCH2CH2OCHO
PhCH(OCHO)Ph
CH3CH(Ph)OCHO
CH3(CH2)4CH(OCHO)CH3
93
93
75
87
85
11, 2,3,4
5, 4
9, 3
—
7, 2, 3, 4
1
1
0
1
90
55
95
92
14
14, 13
1
1
2
3
90
70
7, 13
—
180
Trace
a
1
All products were characterized by comparison of their spectral data ( H NMR, IR) with those of authentic
2
3–26
Samples.
b
Isolated yields.
c
References for previously reported products.
EXPERIMENTAL
ꢀ
ꢀ
Preparation of N,N -Dibromo-N,N –1,2-ethanediylbis(benzene
sulfonamide) [BNBBS]19
To solution of the sulfonamide (50 mmol, 25.0 g), Na2CO3 (25 mmol, 2.65 g), and
KBr (50 mmol) in water (250 mL), a solution of oxone (30.75 g, 50 mmol) in water
◦
(
30 mL) was added slowly at 0 C. After stirring for 24 h at room temperature, the solid
was filtered off, washed with cold distilled water, and dried to give the pure BNBBS.

ACETYLATION AND FORMYLATION OF ALCOHOLS
185
1H NMR (CDCl3), δ (ppm): 3.29 (4H, s), 7.26 (2H, m), 7.55 (4H, m), 7.85 (4H, m);
EIMS: (m/z) = 495 (M+); CHN Anal. Calcd for C14H14Br2N2O4S2: C 33.75, H 2.83, N
5.62, S 12.87. Found: C 33.80, H 2.86, N 5.68, S 12.81.
General Procedure for Acetylation of Alcohols and Phenols
Using Ac2O Catalyzed with BNBBS Under Solvent-Free Conditions
To a solution of alcohol or phenol (1 mmol) and acetic anhydride (1.5 mL), BNBBS
(0.1 mmol, 50 mg) was added, and the mixture was stirred at room temperature for the
specified time (Table I). After completion of the reaction, the reaction was quenched with
saturated NaHCO3 (10 mL). The product was extracted with CH2Cl2 (3 × 10 mL), and the
organic layer was dried over anhydrous Na2SO4. CH2Cl2 was evaporated under reduced
pressure to afford almost pure products. For further purification, the resulting mixture was
applied on a silica gel pad and was washed with a mixture of n-hexane:acetone (10:1).
General Procedure for Formylation of Alcohols Using Formic Acid
Catalyzed with BNBBS Under Solvent-Free Conditions
To a solution of alcohol (1 mmol) and formic acid (2 mL), BNBBS (0.1 mmol, 50 mg)
was added, and the mixture was stirred at room temperature for the specified time (Table II).
After completion of the reaction (TLC), the reaction was quenched with saturated NaHCO3
(
10 mL). The product was extracted with CH2Cl2 (3 × 10 mL), and the organic layer was
dried over anhydrous Na2SO4. The CH2Cl2 was evaporated under reduced pressure to give
almost pure products. In the some cases, the reaction mixture was passed through a short
column of silica gel using n-hexane:acetone (10:1) as an eluent.
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