Selective halogenation of aromatics by dimethyldioxirane and halogen ions

Article abstract of DOI:10.1081/SCC-100105667

The oxidation of halogen anions by dimethyldioxirane (DMD) produced reactive species which led, in acidic media, to the halogenation of activated aromatic rings. The reaction can be efficiently controlled to obtain selective and mixed halogenated species.

Full text of DOI:10.1081/SCC-100105667

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SELECTIVE HALOGENATION OF AROMATICS BY
DIMETHYL-DIOXIRANE AND HALOGEN IONS
Paolo Bovicelli a , Enrico Mincione b , Roberto Antonioletti a , Roberta Bernini b & Maria
Colombari a
a Centro CNR di Studio per la Chimica delle Sostanze Organiche Naturali Dipartimento di
Chimica, Università “La Sapienza” , P.le A. Moro, Box 34 Roma 62, Roma, 5 - 00185, Italy
b Dipartimento A.B.A.C. , Università della Tuscia , Via S. Camillo de Lellis, Viterbo,
01100, Italy
Published online: 16 Aug 2006.
To cite this article: Paolo Bovicelli , Enrico Mincione , Roberto Antonioletti , Roberta Bernini & Maria Colombari (2001)
SELECTIVE HALOGENATION OF AROMATICS BY DIMETHYL-DIOXIRANE AND HALOGEN IONS, Synthetic Communications:
An International Journal for Rapid Communication of Synthetic Organic Chemistry, 31:19, 2955-2963, DOI: 10.1081/
SCC-100105667
To link to this article: http://dx.doi.org/10.1081/SCC-100105667
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SYNTHETIC COMMUNICATIONS, 31(19), 2955–2963 (2001)
SELECTIVE HALOGENATION
OF AROMATICS BY DIMETHYL-
DIOXIRANE AND HALOGEN IONS
Paolo Bovicelli,1, Enrico Mincione,2
*
Roberto Antonioletti,1 Roberta Bernini,2
and Maria Colombari1
1Centro CNR di Studio per la Chimica delle Sostanze
Organiche Naturali Dipartimento di Chimica,
Universita ‘‘La Sapienza,’’ P.le A. Moro,
5 – 00185 Roma – Box 34 Roma 62 – Italy
2Dipartimento A.B.A.C., Universita della Tuscia,
Via S. Camillo de Lellis, 01100 Viterbo, Italy
ABSTRACT
The oxidation of halogen anions by dimethyldioxirane (DMD)
produced reactive species which led, in acidic media, to
the halogenation of activated aromatic rings. The reaction
can be efficiently controlled to obtain selective and mixed
halogenated species.
During our experiments on the selective oxidation of natural sub-
stances by dimethyldioxirane to obtain compounds with potential biological
activities, we observed that dimethyldioxirane (DMD) was able to insert
oxygen into several substrates in a very selective manner.1
*Corresponding author.
2955
Copyright & 2001 by Marcel Dekker, Inc.
www.dekker.com

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BOVICELLI ET AL.
In the case of aromatic compounds activated towards aromatic elec-
trophilic substitutions, the reaction with DMD gave the hydroxylation of
the aromatic rings in moderate yields.2
Proceeding with our research in this field, and with the aim of making
dimethyldioxirane more electrophilic, we performed some tests in acidic
media, obtaining in some cases better yields.
We report now how a different behaviour was observed when hydro-
chloric acid was used as co-solvent: DMD oxidised chloride anions to reac-
tive species which, in acidic medium introduced a halogen atom into
activated sites of aromatic rings.
The importance of aryl halides as precursors of various functional
group transformations makes these compounds valuable for organic syn-
thesis, and their preparation of general interest. Therefore we were
prompted to investigate the reaction to explore their advantages and limits.
In our first experiment resorcinol 1 was selectively transformed in
4-chloro-resorcinol 2, in high yield, by a careful addition of DMD to a
solution of the substrate in hydrochloric acid. The addition of an excess
of DMD to the reaction mixture led, with the same efficiency, to 4,6-
dichloro-resorcinol 5 (Scheme 1).
Scheme 1. Selective chlorination of resorcinol by DMD/HCl system.
The same reaction was then performed using a solution of resorcinol in
hydrobromic or hydroiodic acid. In this case bromo- or iodo-derivatives
were obtained. The selectivity of the process, which led to the insertion of
halogen atoms in the less steric hindered positions, is worthy of note. When
the reaction was carried out in other acidic media, and sodium chloride,
sodium bromide or sodium iodide were used as generators of electrophilic
halogens, the results were exactly the same.
The method was exploited to obtain products with two different halo-
gens in a highly selective procedure.

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2957
In a sulphuric acid diluted solution of resorcinol, an equivalent
amount of sodium bromide and a little excess of dimethyldioxirane were
added. After no more then 10 all the substrate was transformed in 4-bromo-
resorcinol 3. At this step an equivalent amount of sodium chloride and other
portions of dimethyldioxirane were added in succession. The final main
product was 4-chloro-6-bromo-resorcinol 8, which was obtained in very
good yields (Scheme 2).
Scheme 2. Mixed halogenation of resorcinol by DMD/Hþ/NaX system.
The same reaction performed on flavonoid compounds gave the 6,8-
dichloro derivatives in excellent yield, while in absence of halogen ions the
6-hydroxy derivative was obtained (Scheme 3).2
Scheme 3. Halogenation of flavanones by DMD/HCl system.
In the same way we obtained a highly selective functionalisation of
flavones, compounds carrying a double bond in ring B (Scheme 4). In this
case the reaction was chemo-selective. In fact, in neutral conditions or in the
absence of halogen ions, DMD reacts rapidly with the double bond.
The advantage of this system for the preparation of aromatic haloge-
nated compounds is mainly the use of easy manipulating reagents instead of
elementary halogens or more complicated systems,3 together with the easy-
ness of their dosage to prepare mixed halogenated compounds.

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BOVICELLI ET AL.
Scheme 4. Halogenation of flavones by DMD/HCl system.
In the case of mono substituted benzenes such as anisole, there is also
the regioselective aspect to discuss. The chlorination of anisole led to a
mixture of para and ortho chloro-anisole, 14a and 15a in a 5:1 ratio, and
the double chlorination led to the 2,4-dichloro-anisole 16 in a quantitative
yield. No 2,6-dichloro derivative was observed.
The bromination led instead, with an almost complete regiochemical
control, to the para bromo-anisole 14b and the iodination led to low yield of
the corresponding para iodo-anisole 14c (Scheme 5).
Scheme 5. Halogenation of anisole by DMD/Hþ/NaX system.
In nature, halogenated organic compounds are mainly found in
marine organisms.4 This area of natural product chemistry has received

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2959
intense study over the past thirty years. Aromatic halogen compounds have
been found to possess interesting biological activities in many cases. As for
example the highly antimutagenic cymobarbatol,5 some halogenated
indoles6 and carbazoles7 which have a range of antiviral, antimicrobial
and other biological activities including activity against the Polio virus
and Herpes simplex virus.
Ortho halogen phenols are commonly present in nature8 and some of
them are believed to function as a chemical defence to deter potential pre-
dators of the organisms in which they are produced.9 Moreover a large
number of marine metabolites are derived from halogenated tyrosine.10 In
addition chloro-phenols are used industrially on a large scale, and poly-
halogenated phenol derivatives are used in the synthesis of policyclic natural
compounds.11
Given the chemical importance of aromatic halogenated compounds,
principally as synthetic intermediates, our interest is to prosecute the studies
to exploit the selective halogenation of phenols by DMD/HX system for the
synthesis of more interesting compounds.
EXPERIMENTAL
General. 1H- and 13C-NMR spectra were recorded with VARIAN
Gemini 2000 and VARIAN Mercure 300 apparatus in CDCl3. Reactions
were monitored either by TLC using Merck silica gel 60 F-254 plates with
UV indicator or/and visualized with phosphomolybdic acid (10% solution
in EtOH) and by gas chromatography. Flash column chromatography on
silica gel was normally used for purification of the reaction mixtures, when
necessary. Elemental analyses were performed by the Servizio Microanalisi
of the Dip. Chimica of the Universita of Roma ‘‘La Sapienza.’’
Dimethyldioxirane (DMD). A 0.08 M solution of DMD in acetone was
typically prepared as follows. In a 2 l round bottom flask equipped with
a magnetic stirrer, 240 g of OxoneÕ were added in portion to a mixture
of 500 mL of water, 360 mL of acetone and 120 g of sodium hydrogen
carbonate cooled at 0ꢀC and vigorously stirred, during 20–30 min. The sol-
ution was then distilled under vacuum (500 mmHg) taking the collecting
flask at À78ꢀC.
General procedures for the halogenation reactions. Method A. To a
solution of the substrate (0.5 mmol) in acetone (1 mL) and HX (X¼Cl, Br;
10% sol. in water, 1 mL), a 0.08 M solution of DMD in acetone (12–20 mL)
was added during 1 min. Acetone was distilled under vacuum and the mix-
ture extracted with diethyl acetate. Method B. To a solution of the substrate
(0.5 mmol), acetone (1 mL) and H2SO4 (10% sol. in water, 1 mL) and NaX

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BOVICELLI ET AL.
(X¼Cl, Br, 0.5 mmol), a 0.08 M solution of DMD in acetone (12–20 mL)
was added during 1 min. The mixture was worked up as usual.
Dihalogenations. Double halogenations were performed using method A
or method B with an excess of halogen ions and DMD. More substituted
compounds were never observed.
For all the methods, the double halogenation can require more equiva-
lents of the oxidant. This is due to the less reactivity of the monohalo-
genated compounds and the competitive degradation of DMD in acidic
medium. In that case, further portions of DMD solution were added until
disappearance of the starting material (monitoring by GC).
4-Chloro-resorcinol 2a. Method A or B, yield 90%. 1H-NMR, d (ppm):
6.39 (dd, 1H, J ¼ 8.8, 3.3), 6.54 (d, 1H, J ¼ 3.3), 7.15 (d, 1H, J ¼ 8.8).
13C-NMR, d (ppm): 108.8, 111.6, 129.3, 152.1, 155.8.
3-Methoxy-4-chloro-anisole 2b. Method A or B, yield 95%. 1H-NMR,
d (ppm): 3.8 (s, 3H), 3.88 (s, 3H), 6.44 (dd, 1H, J ¼ 8.8, 2.9), 6.49 (d, 1H,
J ¼ 2.9), 7.24 (d, 1H, J ¼ 8.8). 13C-NMR, d (ppm): 55.4, 55.9, 99.9, 105, 113,
130, 155.5, 159.4.
4-Bromo-resorcinol 3a. Method A or B, yield 95%. 1H-NMR, d (ppm):
6.36 (dd, 1H, J ¼ 8.2, 2.7), 6.56 (d, 1H, J ¼ 2.7), 7.25 (d, 1H, J ¼ 8.2).
13C-NMR, d (ppm): 98.1, 103.7, 108.1, 132.5, 154.5, 157.7.
3-Methoxy-4-bromo-anisole 3b. Method A or B, yield 95%. 1H-NMR,
d (ppm): 3.82 (s, 3H), 3.89 (s, 3H), 6.42 (dd, 1H, J ¼ 2.2, 8.8), 6.50 (d, 1H,
J ¼ 2.2), 7.44 (d, 1H, J ¼ 8.8). 13C-NMR, d (ppm): 55.5, 56.1, 99.9, 102.4,
105.9, 133.1, 156.5, 160.2.
3-Methoxy-4-iodo-anisole 4b. Method B, yield 95%. 1H-NMR, d
(ppm): 3.82 (s, 3H), 3.88 (s, 3H), 6.33 (dd, 1H, J ¼ 2.2, 8.8), 6.45 (d, 1H,
J ¼ 2.2), 7.65 (d, 1H, J ¼ 8.8). 13C-NMR, d (ppm): 55.5, 56.2, 74.7, 99.2,
106.9, 139.1, 158.8, 161.3.
1
4,6-Dichloro-resorcinol 5a. Method A or B, yield 85%. H-NMR, d
(ppm): 6.72 (s, 1H), 7.28 (s, 1H). 13C-NMR, d (ppm): 103.9, 110, 126.2, 151.4.
3-Methoxy-4,6-dichloro-anisole 5b. Method A or B, yield 90%.
1H-NMR, d (ppm): 3.86 (s, 6H), 6.49 (s, 1H), 7.28 (s, 1H). 13C-NMR, d
(ppm): 56.2, 97.5, 113.6, 130.1, 154.3.
1
4,6-Dibromo-resorcinol 6a. Method A or B, yield 78%. H-NMR, d
(ppm): 5.48 (br, 2H), 6.74 (s, 1H), 7.53 (s, 1H). 13C-NMR, d (ppm): 98.7,
103.1, 134.5, 151.6.
3-Methoxy-4,6-dibromo-anisole 6b. Method A or B, yield 85%.
1H-NMR, d (ppm): 3.89 (s, 6H), 6.48 (s, 1H), 7.65 (s, 1H). 13C-NMR, d
(ppm): 56.5, 97.46, 102.46, 135.9, 156.1.
1
3-Methoxy-4,6-diiodo-anisole 7b. Method B, yield 90%. H-NMR, d
(ppm): 3.88 (s, 6H), 6.36 (s, 1H), 8.03 (s, 1H). 13C-NMR, d (ppm): 56.5, 75.5,
95.9, 146.8, 159.6.

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2961
4-Bromo-6-chloro-resorcinol 8. Method B was used for the preparation
of 3a, then 1 eq. of NaCl and an other amount of DMD were added to the
mixture. After additions were completed, the usual work up gave 8 which
1
resulted pure from NMR analysis. H-NMR, d (ppm): 3.90 (s, 3H), 3.91 (s,
3H), 6.50 (s, 1H), 7.49 (s, 1H). 13C-NMR, d (ppm): 56.3, 56.5, 97.5, 101.8,
114.4, 113.1, 135.8, 155.1. Analysis: calc. for C6H4BrClO2 C 32.25, H 1.80;
found C 32.3, H 2.0.
5,7,40-Trimethoxy-6,8-dichloro-flavanone 10. Method A, quant. yield.
1H-NMR, d (ppm): 2.88 (dd, 1H, J ¼ 3, 16.4), 3.07 (dd, 1H, J ¼ 13, 16.4),
3.81 (s, 3H), 3.89 (s, 3H), 3.96 (s, 3H), 5.48 (dd, 1H, J ¼ 3, 13), 6.93 (d, 1H,
J ¼ 5.5), 7.39 (d, 1H, 5.5). 44.8, 55.3, 60.9, 61.8, 79.3, 113.4, 114.2, 127.5,
129.7, 156.0, 157.4, 158.5, 160.0, 188.6. Analysis: calc. for C18H16Cl2O5 C
56.41, H 4.21; found C 56.2, H 4.5.
5,7-Dihydroxy-6,8-dichloro-flavone 12a. Method A, yield 72%.
1H-NMR (DMSO-d6), d (ppm): 7.16 (s, 1H), 7.52–7.68 (m, 3H), 8.08–8.18
(m, 2H). 99.4, 103.9, 104.5, 105.3, 126.4, 129.3, 130.2, 132.5, 155.1, 155.9,
161.6, 163.5, 170.9, 181.7. Analysis: calc. for C15H8Cl2O4 C 55.76, H 2.5;
found C 55.9, H 2.8.
5,7-Dimethoxy-6,8-dichloro-flavone 12b. Method A, yield 87%.
1H-NMR, d (ppm): 3.99 (s, 3H), 4.04 (s, 3H), 6.77 (s, 1H), 7.48–7.60 (m,
3H), 7.90–8.20 (m, 2H). 13C-NMR, d (ppm): 61.2, 62.1, 108.3, 14.2, 16.5,
121.5, 126.1, 129.1, 130.6, 131.9, 152.2, 154.8, 156.9, 161.5, 175.9. Analysis:
calc. for C17H12Cl2O4 C 58.14, H 3.44; found C 57.8, H 3.4.
1
4-Chloro-anisole 14a. Method B, yield 82%. H-NMR, d (ppm): 3.81
(s, 3H), 6.84 (bd, 2H, J ¼ 9.5), 7.26 (bd, 2H, J ¼ 9.5). 13C-NMR, d (ppm):
55.4, 115.1, 127.7, 129.3, 158.2.
4-Bromo-anisole 14b. Method B, yield 96%. By NMR analysis of the
crude, 1.3% of 2-bromo-anisole was also detected. An excess of DMD did
1
not give the dibromo derivative in any condition. H-NMR, d (ppm): 3.80
(s, 3H), 6.78 (bd, 2H, J ¼ 9.2), 7.38 (bd, 2H, J ¼ 9.2). 13C-NMR, d (ppm):
55.4, 112.8, 115.7, 132.2, 158.7.
4-Iodo-anisole 14c. Method B, yield 30%. Further additions of DMD
1
resulted in decomposition of the mixture. H-NMR, d (ppm): 3.79 (s, 3H),
6.78 (bd, 2H, J ¼ 9.4), 7.55 (bd, 2H, J ¼ 9.4). 13C-NMR, d (ppm): 55.3, 82.7,
116.4, 138.2, 159.5.
1
2-Chloro-anisole 15a. Method B, yield 13%. H-NMR, d (ppm): 3.89
(s, 3H), 6.89 (m, 2H), 7.21 (m, 1H), 7.4 (dd, 1H, J ¼ 2.2, 8.1).
1H-NMR, d (ppm): 13C-NMR, d (ppm): 56.0, 112.1, 121.2, 125.5, 127.5,
130.2, 155.0.
1
2,4-Dichloro-anisole 16a. Method B, yield 96%. H-NMR, d (ppm):
3.9 (s, 3H), 6.86 (d, 1H, J ¼ 8.8), 7.22 (dd, 1H, J ¼ 2.2, 8.8), 7.38 (d, 1H,
J ¼ 2.2). 13C-NMR, d (ppm): 56.3, 112.8, 123.3, 125.6, 127.6, 129.9, 153.9.

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BOVICELLI ET AL.
2-Chloro-4-bromo-anisole 16b. Method B, yield 87%. 1H-NMR, d
(ppm): 3.81 (s, 3H), 6.72 (d, 1H, J ¼ 8.8), 7.26 (dd, 1H, J ¼ 2.2, 8.8), 7.42 (d,
1H, J ¼ 2.2). 13C-NMR, d (ppm): 56.2, 112.4, 113.3, 123.6, 130.4, 132.6, 154.3.
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Received in the UK September 22, 2000

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