Selective conversion of epoxides to vic-halo alcohols and symmetrical or unsymmetrical dihalides by triphenylphosphine/2,3-dichloro-5,6-dicyano-1,4- benzoquinone (DDQ) in the presence of quaternary ammonium halides

Article abstract of DOI:10.1246/bcsj.77.1885

A new method is described for the efficient and selective conversion of epoxides to vic-halo alcohols or symmetrical and unsymmetrical dihalides using PPh₃/DDQ/R₄NX (X = Cl, Br, I) as a mixed-reagent system.

Full text of DOI:10.1246/bcsj.77.1885

Ó 2004 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 77, 1885–1891 (2004) 1885
Selective Conversion of Epoxides to vic-Halo Alcohols and Symmetrical
or Unsymmetrical Dihalides by Triphenylphosphine/2,3-Dichloro-5,6-
dicyano-1,4-benzoquinone (DDQ) in the Presence of Quaternary
Ammonium Halides
ꢀ
ꢀ
Nasser Iranpoor, Habib Firouzabadi, Ghasem Aghapour, and Azarmidokht Nahid
Chemistry Department, College of Sciences, Shiraz University, Shiraz 71454, Iran
Received July 29, 2003; E-mail: iranpoor@chem.susc.ac.ir
A new method is described for the efficient and selective conversion of epoxides to vic-halo alcohols or symmet-
rical and unsymmetrical dihalides using PPh3/DDQ/R4NX (X = Cl, Br, I) as a mixed-reagent system.
Epoxides are important intermediates in organic synthesis.1
PPh3/DDQ/n-Bu4NBr
Their facile regio- and stereoselective ring-opening reactions
with a wide variety of nucleophiles provide a powerful strat-
egy in organic chemistry.1–6 One of the useful nucleophilic re-
actions of epoxides is their conversion into their vic-halo alco-
hols.7–11 In order to avoid the use of strongly acidic hydrogen
halides for their synthesis,12 different methodologies have been
developed in recent years. Some of these methods are consid-
ered, such as the use of magnesium nitrate,13 or ammonium
cerium(IV) nitrate in the presence of halide ions,14 phosphafer-
rocene as a catalyst with TMSCl,15 silica gel in the presence of
lithium halides,16 2-phenyl-2-(2-pyridyl)imidazolidine (PPI) in
the presence of elemental halogens,17 iron(III) trifluoroacetate
with quaternary ammonium halides or their ammonium salts,18
PPh3/CBr4,19 phenylhydrazine in the presence of elemental
halogens,20 and crown ethers/elemental halogens.21 The con-
version of epoxides to symmetrical vic-dihalides as another
important route for the preparation of halogenated compounds
(1.2/1.2/1.2)
PhOCH2CH(OH)CH2Br
(b)
CH3CN, reflux, 30 min
PhO
O
PPh3/DDQ/n-Bu4NBr
PhOCH2CHBrCH2Br
(c)
(a)
(1.2/1.2/2.2)
CH3CN, reflux, 2h
Scheme 1.
Table 1. Various Reaction Conditions for the Conversion
of Oxiranylmethyl Phenyl Ether (a) with PPh3/DDQ/
n-Bu4NBr to Its vic-Bromo Alcohol (b) or vic-Dibromide
(c) in Refluxing Acetonitrile
Entry
Time/h
Yield/%
1iÞ
0.5
0.5
12
3.75
0.5
2.0
20
55 of (b) + 25 of (c)
0
2iiÞ
3iiiÞ
4ivÞ
5vÞ
6viÞ
95 of (b)
97 of (b)
90 of (c)
22
with reagents, such as PPh3/CCl4 and PPh3/X2 (X = Cl,
Br),23 are also reported in the literature.
Although there are reports concerning the preparation of un-
symmetrical vic-dihalides from alkenes,24–26 as far as we know
there is only one method described in the literature about the
preparation of unsymmetrical vic-dihalides from epoxides.23
By this method, epoxide was firstly converted to its corre-
sponding vic-halo alcohol under highly acidic conditions using
HCl/THF, followed by a treatment with PPh3/Br2 to convert
the hydroxy group into bromide.
In continuation of our recent work on the use of PPh3/
DDQ/R4NX,27 we now report on a new and highly selective
method for the conversion of epoxides to either vic-halo alco-
hols and vic-symmetrical or unsymmetrical dihalides using this
mixed-reagent system.
In this article, we report that epoxides in the presence of
PPh3/DDQ/R4NX (X = Cl, Br, I) can be converted to vic-halo
alcohols or vic-dihalides, depending on the molar ratio of the
reagents to the epoxides (Scheme 1).
We took oxiranylmethyl phenyl ether as an example, and
optimized the reaction conditions for its conversion to vic-halo
i) Epoxide (one equimolar) is added to the mixture of PPh3/
DDQ/n-Bu4NBr with molar ratio of 1.2/1.2/1.2 at room tem-
perature. ii) Reaction is performed in refluxing acetonitrile. iii)
Reaction is performed in the absence of PPh3/DDQ. iv) n-
Bu4NBr is gradually added to the refluxing mixture of
Ph3P/DDQ over 3.5 h and then refluxed for additional 0.5 h
(see experimental section, method A). v) Reaction is carried
out in the presence of 0.5 molar equivalent of water (see ex-
perimental section, method B). vi) This experiment is per-
formed in refluxing acetonitrile, and the molar ratio of
PPh3/DDQ/n-Bu4NBr is 1.2/1.2/2.2.
alcohols or vic-dibromides using different molar ratios of
PPh3/DDQ/n-Bu4NBr in refluxing acetonitrile. It was ob-
served that the molar ratios of 1.2/1.2/1.2 and 1.2/1.2/2.2
of this mixed reagent system produced the highest yield of
the corresponding vic-halo alcohol and vic-dibromide, respec-
tively. The optimized reaction conditions are given in Table 1.
As shown in Table 1, the reaction of oxiranylmethyl phenyl
Published on the web October 9, 2004; DOI 10.1246/bcsj.77.1885

1886 Bull. Chem. Soc. Jpn., 77, No. 10 (2004)
Synthesis of vic-Halo Alcohols and Dihalides
Table 2. Conversion of Epoxides to vic-Halo Alcohols with PPh3/DDQ/R4NX (X = Cl, Br, I) (1.2/1.2/1.2) in Refluxing AcetonitrileaÞ
Entry
1
Substrate
Productb)
Yieldc)
95d)
%
Entry
10
Substrate
Productb)
Yieldc)
96d)
%
O
(1)
(8)
O
OH
O
O
OH
PhO
PhO
PhO
O
O
Br
Cl
(2)
(3)
O
OH
O
O
OH
O
O
75d)
70d)
11
12
87d)
90d)
2
3
4
PhO
PhO
O
O
Cl
O
Br
I
O
OH
(9)
OH
O
O
PhO
Cl
I
O
OH
O
O
75 (15)e)
65 (15)d)
OH
13
14
88d)
78d)
O
Ph
OH
Ph
Ph
Cl
Ph
Ph
Cl
OH
Br
(4)
(5)
OH
I
O
O
O
5
Ph
OH
I
O
(6)
(7)
OH
OH
Br
OH
Br
60 (35)c)
15
16
80d)
95d)
6
7
Ph
O
Ph
OH Ph
OH
Br
O
94d,e)
O
Cl
OH
I
O
87d)
95d)
Cl
8
9
O
O
17
18
78
O
Br
OH
OH
O
Ph
90d)
erythro-PhCHOHCHBrPh
O
O
Ph
I
O
a) Method A is applied. b) All the products are known compounds14,17,18,21,28 and are identified by their physical or spectral data. c)
Isolated yield. d) Method B is used. Reaction time for all epoxides is 0.5 h except trans-stilbene and cyclopentene oxides which require
3 h. e) Yield is based on GC and NMR analysis.
ether (a) with a mixture of PPh3/DDQ/n-Bu4NBr at room
temperature afforded 1-bromo-3-phenoxy-2-propanol (b) in
only 20% after 0.5 h (Table 1, entry 1). However, in refluxing
acetonitrile, the rate of the reaction was increased, and the de-
sired product was obtained in 55% yield after 0.5 h, together
with 1,2-dibromo-3-phenoxypropane (c) in 25% yield
(Table 1, entry 2). A quantitative yield of the desired halo al-
cohol was obtained when the halide ion (1.2 mol. amt.) was
gradually added into the reaction mixture of epoxide and
PPh3/DDQ (1.2:1.2) in refluxing acetonitrile over a period
of about 3.5 h, and then refluxed for an additional 0.5 h. Under
these conditions, 1-bromo-3-phenoxy-2-propanol (b) was ob-
tained in 95% yield (Table 1, entry 4). Also, our studies
showed that the addition of a 0.5 molar equivalent of water
to a mixture of epoxide and PPh3/DDQ/n-Bu4NBr (1.2:1.2:
1.2) in refluxing acetonitrile caused the reaction rate to in-
crease, and the desired halo alcohol (Scheme 1, b) was ob-
tained in 97% yield after 0.5 h (Table 1, entry 5). However,
in the absence of PPh3 and DDQ, the epoxide did not react
with n-Bu4NBr, even after 12 h of refluxing (Table 1, entry
3). By increasing the amount of n-Bu4NBr from 1.2 molar
amounts to 2.2, the corresponding vic-dibromide was produced
in 90% yield (Scheme 1, c, Table 1, entry 6).
We then applied the optimized reaction conditions of
Table 1 (entries 4 or 5, methods A or B respectively, see ex-
perimental section), for the conversion of structurally different
epoxides to their corresponding vic-halo alcohols. The results
are given in Table 2.
Under these reaction conditions, the ethereal bonds, ester
groups, and carbon–carbon double bonds as functional groups
that are present in the epoxide molecules remained intact. Ex-
cept for the case of styrene oxide, which produced two regio-
isomers (Table 2, entries 4–6), the reaction of other unsymmet-
rical epoxides occurred with high regioselectivity, and the hal-
ide anion attacked at the less-hindered side of the epoxide ring
due to the combination of steric and electronic factors. The re-
action of trans-stilbene oxide (Table 2, entry 18) as an exam-
ple of a hindered disubstituted epoxide completed after 3 h and
erythro-2-bromo-1,2-diphenylethanol28 was obtained in 90%
yield. The reaction of cyclopentene oxide was also found to
be slower than the reaction of cyclohexene oxide (Table 2,
entry 15).

N. Iranpoor et al.
Bull. Chem. Soc. Jpn., 77, No. 10 (2004) 1887
was confirmed by its 1H, 13C NMR and mass spectral data.
Since this attempt was successful, we applied it to the prepa-
ration of unsymmetrical vic-dihalides from other epoxides.
By using proper halide anions in each step, we cauld easily
control the formation of vic-dihalides with high regioselectiv-
ity. The results obtained for this study are given in Table 4.
In these reactions, as we expected, in the first step, the pri-
marily used halide ion attacks the epoxide ring from its less-
hindered side, similar to the formation of vic-halo alcohols.
In the second step, the resulting halo alcohol reacts with the
mixture of PPh3/DDQ in the presence of the second halide
anion to displace the hydroxy group to produce the desired un-
symmetrical dihalide. It was observed that, when one of the
nucleophiles was iodide, due to the possibility of the elimina-
tion of IX; (X = Cl, Br), alkene formation was a competing
pathway, which lowered the yield of vic-dihalides considera-
bly (Table 4, entries 3 and 6).
Although, the exact mechanism of these reactions is not
clear, we may suggest that at first, a positively charged adduct
I is formed from the reaction of PPh3 with DDQ27 (Scheme 2).
This positively charged adduct can then activate the epoxide
ring through an interaction with its oxygen atom so that halide
ion can attack this activated ring and produce the intermediate
II. The attack of another halide ion could convert the inter-
mediate II into the desired symmetrical or unsymmetrical
vic-dihalide (path a). The hydrolysis of II in the workup pro-
cedure produces triphenylphosphine oxide and the correspond-
ing vic-halo alcohol (path b). Also, in the case of using hydrat-
ed quaternary ammonium halides (method B), the hydrated
water hydrolyzes the intermediate (II) to halo alcohol (path
b). In this case, for converting the produced halo alcohol to
vic-dihalides, excess PPh3 and DDQ are required, since the ad-
duct (I) which is produced in this stage can be partly hydro-
lyzed with the hydrated water.
As shown in Table 4, entries 2, 4, when the first nucleophile
used was bromide, a mixture of two regio-isomers were ob-
tained. It is assumed that in these cases, the intermediate I
can release OPPh3 through the anchimeric assistance of bro-
mide to form the bromonium ion II which can be equilibrated
with III (Scheme 3). Attacking the second nucleophile to
either side of II can produce a mixture of two regio-isomers.
This phenomenon can also be observed in the conversion of
cyclohexene oxide to trans-1,2-dibromocyclohexane instead of
its cis-isomer (Table 3, entry 7). Cyclohexene oxide in the first
step can interact with the adduct complex of PPh3/DDQ to
form the intermediate I. The attack of Brꢁ to I produces the
trans-intermediate II. The attack of the second Brꢁ converts
the intermediate II to the corresponding cis-vic-dibromides
(path a). However, our observation showed that the actual
pathway of reaction is path (b). This is evidenced by the for-
mation of trans-vic-dibromide, which can occur through the
bromonium ion intermediate III (Scheme 4).
O+PPh3
O
R
Cl
Cl
CN
+
Cl
CN
PPh3
O
CN
Cl
CN
O
(I)
O-
RCHXCH2X + PPh3O
ArO-PPh3
+O
path (a)
X
ArO-PPh3
-
O
+ X_
path (b)
R
X
R
(II)
H2O
X-
RCH(OH)CH2X
/DDQ
RCHXCH2X
ess PPh3
c
ex
Scheme 2.
In order to obtain vic-dihalides, epoxides were reacted with
a mixture of PPh3/DDQ/n-R4NX (R = Bu, X = Br, I; R =
Hex, X = Cl) using the optimized molar ratio of 1.2/1.2/2.2
in refluxing acetonitrile. The use of bromide and chloride
anions in this method offers the possibility of having vic-di-
chlorides and dibromides under mild and neutral reaction con-
ditions. In contrast with reagents such as PPh3/Br2 or PPh3/
CCl4, our reagent system does not produce any electrophilic
halogen in the reaction mixture. This gives the advantage that
activated aromatic rings and double bonds remain intact during
the reaction, and only the epoxide ring reacts. For preparing
vic-dichlorides from epoxides, in addition to n-Hex4NCl, hy-
drated n-Bu4NCl can also be used as the source of halide
anion, but due to the presence of water in the reaction mixture,
which can destroy the adduct (I, Scheme 2), the required
amounts of PPh3 and DDQ are increased (see experimental
section, method B). The results of this investigation are given
in Table 3.
However, the preparation of vic-diiodide was not successful.
This observation is in accordance with the literature data,29
which show that alkene formation is favored due to the easy
elimination of molecular iodine from their corresponding diio-
dides. In all of the reactions with Iꢁ, the alkene formation was
the major pathway and the corresponding alkenes were ob-
tained in high yields. For example, the addition of oxiranyl-
methyl phenyl ether to the mixture of PPh3/DDQ/n-Bu4NI
(1.2:1.2:2.2) in refluxing acetonitrile produced allyl phenyl
ether as the major product (90%) after 0.5 h. Therefore, the
use of a PPh3/DDQ mixture in the presence of n-Bu4NI offers
a new mixed-reagent system for the deoxygenation of epoxides
into their corresponding alkenes.
In order to overcome the problems of using the highly acidic
conditions reported for the conversion of epoxides to vic-dihal-
ides,27 and to introduce a mild and novel method for this trans-
formation, we decided to apply our procedure for this prepara-
tion by a successive use of two different halide ions. For this
purpose, first, oxiranylmethyl phenyl ether was added to a mix-
ture of PPh3/DDQ/n-Bu4NCl H2O with a stoichiometry ratio
ꢂ
of (1.2:1.2:1.2). Then, the reaction mixture was refluxed to
produce 1-chloro-3-phenoxy-2-propanol (2). When all of the
epoxide was consumed, the mixture was poured to another
mixture containing (PPh3/DDQ/n-Bu4NBr (2.3:2.3:1.2) in
acetonitrile and refluxed for another 0.5 h. After completion
of the reaction, 2-bromo-1-chloro-3-phenoxypropane (13)
was obtained in 81% yield (Table 4, entry 1) and its structure
In summary, the present investigation has demonstrated that
the use of the PPh3/DDQ/R4NX system offers a simple, nov-
el, and convenient method for the selective conversion of ep-
oxides to either their corresponding vic-halo alcohols or sym-
metrical vic-dihalides. Also, vic-dihalides containing two dif-
ferent types of halides with the desired regiochemistry can
be produced easily by the use of this mixed-reagent system.

1888 Bull. Chem. Soc. Jpn., 77, No. 10 (2004)
Synthesis of vic-Halo Alcohols and Dihalides
Table 3. Conversion of Epoxides to vic-Dihalides by PPh3/DDQ in the Presence of R4NX
(R = n-Bu or n-Hex, X = Cl, Br)aÞ
Entry
Substrate
Productb)
Isolated and
(conversion)c)
Yield %
Br
(10)
(11)
O
O
PhO
PhO
1
80 (90)
PhO
PhO
Br
Cl
2
3
78 (97)
70 (85)
Cl
Cl
O
Ph
Br
Cl
Ph
(12)
(13)
O
4
5
77 (92)
85 (90)
Ph
Ph
Br
Br
O
O
O
Br
Br
(14)
Br
O
O
O
6
7
8
74 (85)
70 (83)
67 (93)d)
O
O
Br
Br
Br
Br
O
O
O
O
Br
Cl
9
72 (88)
Br
10
11
(80)
Cl
Br
Br
84 (93)
O
Ph
12
erythro-PhCHBrCHBrPh
86 (94)d)
Ph
O
a) Methods A and B are used for the preparation of dibromides and dichlorides respectively.
b) The products of entries 7–12 are known compounds.28 c) Conversion yield is based on GC
and NMR analysis using internal standard. (d) Reaction times for trans-stilbene and cyclopen-
tene oxides are more than other epoxides (see experimental section).
Nuclear magnetic resonance spectra were recorded on Hitachi R-
Experimental
245 and Brucker Avance DPX-250 spectrometers. Mass spectra
were determined on a Shimadzu GCMS-QP 1000 EX at 70 eV.
General Procedure for the Conversion of Epoxides to vic-
Halo Alcohols. Method A: To a flask containing of PPh3
Solvents, reagents, and chemicals were obtained from Merck
(Germany) Fluka (Switzerland) Chemical Companies. Infrared
spectra were recorded on a Perkin Elmer 781 spectrophotometer.

N. Iranpoor et al.
Bull. Chem. Soc. Jpn., 77, No. 10 (2004) 1889
Table 4. Conversion of Epoxides to Unsymmetrical vic-Di-
halides by PPh3/DDQ and Quaternary Ammonium Salts
of Different Halides
Y
Br
O Ar
R
(II)
O PPh3
Br
R
Y
Entry
1
Substrate
O
Product
Br
Yielda)
%
-OPPh
3
Br
R
(I)
(15)
Br
81
PhO
PhO
Br
R
(III)
Cl
Y
R
(16)
O
O
Cl
Scheme 3.
2
3
4
5
65b)
PhO
PhO
PhO
Br
(17)
OPPh3(OAr)
+
Br-
I
PPh3/DDQ
O
O
PPh3
OAr
40
PhO
Br
Cl
Br-
(I)
(II)
path (a)
(18)
O
O
Cl
O
O
O
63b)
72
Br
Br
Br
Br
O
O
Br
+
(19)
Br-
Br
O
O
Br
O
(III)
Cl
Scheme 4.
(20)
Cl
O
6
55
I
of DDQ (1.2 mmol) in refluxing acetonitrile (15 mL). Quaternary
ammonium halide monohydrate (2.2 mmol) and epoxide (1 mmol)
were added to this reaction mixture. A TLC or GC analysis
showed the completion of the conversion of epoxide to vic-halo
alcohol after 30 min. Then, the reaction mixture was transferred
to another mixture containing PPh3 (2.3–2.8 mmol) and DDQ
(2.3–2.8 mmol) in acetonitrile (10 mL) and refluxed for 0.5 h to
produce vic-dihalide. The solvent was then evaporated. vic-Dihal-
ide was obtained after column chromatography of the crude mix-
ture using petroleum ether as an eluent in 65–85% yield (Table 3).
General Procedure for the Conversion of Epoxides to Un-
a) Isolated yield. b) The other isomeric product was formed
about 20% yield in this case.
(1.2 mmol) and DDQ (1.2 mmol) in refluxing acetonitrile (7 mL)
was added epoxide (1 mmol). Then, a solution of quaternary am-
monium halide (1.2 mmol) in acetonitrile (5 mL) was gradually
added to the reaction mixture over a period of 3.5 h. TLC or
GC analysis showed completion of the reaction after 4 h. The sol-
vent was evaporated. Pure vic-halo alcohol was obtained in 70–
96% yields after column chromatography of the crude mixture
on silica gel using petroleum ether/ethyl acetate as an eluent
(Table 2).
Method B: Quaternary ammonium halide (1.2 mmol) and
H2O (1 mmol) were added to a flask containing of PPh3 (1.2
mmol) and DDQ (1.2 mmol) in refluxing acetonitrile (10 mL), re-
spectively. Then, epoxide (1 mmol) was added to the reaction
mixture. TLC monitoring showed completion of the reaction after
30 min. The solvent was evaporated. The corresponding vic-halo
alcohol was obtained in good to excellent yields after column
chromatography of the crude product on silica gel using petroleum
ether/ethyl acetate as an eluent (Table 2).
General Procedure for the Conversion of Epoxides to Sym-
metrical vic-Dihalides. Method A: Anhydrous quaternary am-
monium halide (2.2 mmol) was added to a flask containing of
PPh3 (1.2 mmol) and DDQ (1.2 mmol) in refluxing acetonitrile
(15 mL). Then, epoxide (1 mmol) was added to the reaction mix-
ture. TLC or GC analysis showed completion of the reaction after
2 h (in the case of trans-stilbene and cyclopentene oxides, the re-
action mixtures were refluxed for 9 and 4 h, respectievly). After
evaporation of the solvent, the crude mixture was purified by col-
umn chromatography using petroleum ether as an eluent to give
vic-dihalide in 65–85% yield (Table 3).
symmetrical vic-Dihalides.
A mixture of PPh3 (1.2 mmol)
and DDQ (1.2 mmol) was prepared in refluxing acetonitrile (10
mL). Then, quaternary ammonium halide monohydrate (1.2
mmol) and epoxide (1 mmol) were added to this mixture. TLC
or GC analysis showed the conversion of the epoxide to the cor-
responding vic-halo alcohol after 0.5 h. The reaction mixture
was then transferred to another flask containing PPh3 (2.8 mmol),
DDQ (2.8 mmol) and the tetraalkylammonium salt of the desired
halide anion (1.2 mmol) in acetonitrle (15 mL) and refluxed for
0.5 h to produce vic-dihalide. After evaporation of the solvent,
vic-dihalide was obtained in 40–81% yield by column chromatog-
raphy of the crude mixture using petroleum ether as an eluent
(Table 4).
All of the new products gave satisfactory elemental analysis.
The spectral data of some of the products are shown below:
1-Bromo-3-phenoxy-2-propanol (1): 1H NMR (CDCl3, 250
MHz) ꢀ 2.59–2.61 (d, 1H, J ¼ 5 Hz), 3.58–3.69 (m, 2H), 4.07–
4.10 (m, 2H), 4.14–4.23 (m, 1H), 6.90–7.10 (m, 3H), 7.26–7.54
(m, 1H); 13C NMR (CDCl3, 62.9 MHz) ꢀ 35.04, 69.50, 70.27,
114.54, 121.45, 129.59, 158.13; Mass spectra m=e: 232 (M þ 2,
33.1%), 230 (M, 35.6%), 151 (M ꢁ Br, 20.3%).
1-Chloro-3-phenoxy-2-propanol (2): 1H NMR (CDCl3, 250
MHz) ꢀ 2.64–2.66 (d, 1H, J ¼ 5 Hz), 3.68–3.81 (m, 2H), 3.98–
4.08 (m, 2H), 4.12–4.22 (m, 1H), 6.89–7.01 (m, 3H), 7.24–7.32
Method B: PPh3 (1.2 mmol) was added to a flask containing

1890 Bull. Chem. Soc. Jpn., 77, No. 10 (2004)
Synthesis of vic-Halo Alcohols and Dihalides
(m, 2H); 13C NMR (CDCl3, 62.9 MHz) ꢀ 46.37, 68.79, 70.29,
114.94, 121.86, 130.01, 158.08; Mass spectra m=e: 188 (M þ 2,
34.9%), 186 (M, 100%), 169 (M ꢁ OH).
2,3-Dibromopropyl 2-Methacrylate (14): 1H NMR (CDCl3,
250 MHz) ꢀ 1.89 (s, 3H), 3.71–3.74 (d, 2H, J ¼ 7:5 Hz), 4.17–
4.26 (m, 1H), 4.33–4.46 (m, 2H), 5.56 (s, 1H), 6.09 (s, 1H); Mass
spectra m=e: 288 (M þ 4, 2.1%), 286 (M þ 2, 2.5%), 284 (M,
1%), 207 (M þ 4 ꢁ Br, 9%), 205 (M ꢁ Br, 10%).
1-Iodo-3-phenoxy-2-propanol (3):
1H NMR (CDCl3, 250
MHz) ꢀ 2.57 (s, 1H), 3.38–3.50 (m, 2H), 3.97–4.0 (m, 1H),
4.05–4.1 (m, 2H), 6.90–7.01 (m, 3H), 7.25–7.33 (m, 2H);
13C NMR (CDCl3, 62.9 MHz) ꢀ 9.15, 69.55, 70.29, 114.58,
121.46, 129.60, 158.16; Mass spectra m=e: 278 (M, 25.7%), 151
(M ꢁ I, 6.7%), 133 (M ꢁ (I + H2O), 27.1%).
2-Bromo-1-chloro-3-phenoxypropane (15):
1H NMR
(CDCl3, 250 MHz) ꢀ 3.92–4.02 (m, 2H), 4.25–4.39 (m, 3H),
6.83–7.07 (m, 3H), 7.23–7.33 (m, 2H); 13C NMR (CDCl3, 62.9
MHz) ꢀ 45.01, 48.10, 68.26, 114.79, 121.66, 129.61, 157.92; Mass
spectra m=e: 252 (M þ 4, 8.7%), 250 (M þ 2, 29.3%), 248 (M,
24%), 171 (M þ 2 ꢁ Br and M þ 4 ꢁ Br, 7.2%), 169 (M þ 2
ꢁ Br and M ꢁ Br, 12.9%).
2-Iodo-2-phenylethanol (4): 1H NMR (CDCl3, 250 MHz) ꢀ
2.04 (s, 1H), 3.92 (s, 1H), 4.09 (s, 1H), 5.17–5.23 (t, 1H, J ¼
7:5 Hz), 7.25–7.44 (m, 5H); 13C NMR (CDCl3, 62.9 MHz) ꢀ
35.78, 68.62, 127.91, 128.61, 129.0, 142.4; Mass spectra m=e:
248 (M, 0.1%), 231 (M ꢁ OH, 22.2%), 121 (M ꢁ I, 100%).
2-Iodo-1-phenylethanol (5): 1H NMR (CDCl3, 250 MHz) ꢀ
2.50 (s, 1H), 3.36–3.52 (m, 2H), 4.82–4.85 (m, 1H), 7.36 (s,
5H); 13C NMR (CDCl3, 62.9 MHz) ꢀ 15.78, 74.45, 126.14,
128.79, 129.11, 141.5; Mass spectra m=e: 248 (M, 0.5%), 231
(M ꢁ OH, 1.9%), 121 (M ꢁ I, 9.3%).
1-Bromo-2-chloro-3-phenoxypropane (16):
1H NMR
(CDCl3, 250 MHz) ꢀ 3.77–3.95 (m, 2H), 4.25–4.37 (m, 3H),
6.91–7.02 (m, 3H), 7.23–7.33 (m, 2H); 13C NMR (CDCl3, 62.9
MHz) ꢀ 33.36, 57.40, 69.29, 115.18, 122.09, 130.04, 158.37; Mass
spectra m=e: 250 (M þ 2, 0.8%), 248 (M, 0.4%), 169 (M þ 2 ꢁ Br
and M ꢁ Br, 7%).
1-Chloro-2-iodo-3-phenoxypropane (17): 1H NMR (CDCl3,
250 MHz) ꢀ 3.90–4.05 (m, 2H), 4.26–4.36 (m, 3H), 6.91–7.02 (m,
3H), 7.24–7.33 (m, 2H); 13C NMR (CDCl3, 62.9 MHz) ꢀ 29.70,
45.02, 68.10, 114.71, 121.67, 129.62, 158.02; Mass spectra m=e:
298 (M þ 2, 9.2%), 296 (M, 26.3%), 261 (M ꢁ Cl, 5.4%), 169
(M ꢁ I, 15.3%).
2-Bromo-2-phenylethanol (6): 1H NMR (CDCl3, 250 MHz)
ꢀ 2.08 (s, 1H), 3.93–4.10 (m, 2H), 5.02–5.08 (t, 1H, J ¼ 7:5 Hz),
7.25–7.43 (m, 5H); 13C NMR (CDCl3, 62.9 MHz) ꢀ 56.95, 67.53,
127.92, 128.90, 128.99, 138.21; Mass spectra m=e: 202 (M þ 2,
5.2%), 200 (M, 0.9%), 183 (M ꢁ OH, 27.4%), 121 (M ꢁ Br,
100%).
3-Bromo-2-chloropropyl Methacrylate (18):
1H NMR
2-Bromo-1-phenylethanol (7): 1H NMR (CDCl3, 250 MHz)
ꢀ 2.66 (s, 1H), 3.50–3.66 (m, 2H), 4.94 (s, 1H), 7.37–7.38 (s, 5H);
13C NMR (CDCl3, 62.9 MHz) ꢀ 40.65, 74.22, 126.37, 128.89,
129.1; Mass spectra m=e: 202 (M þ 2, 0.6%), 200 (M, 0.4%),
183 (M ꢁ OH, 2.8%), 121 (M ꢁ Br, 4.1%).
(CDCl3, 250 MHz) ꢀ 1.97 (s, 3H), 3.66–3.91 (m, 2H), 4.32–
4.58 (m, 3H), 5.64 (s, 1H), 6.18 (s, 1H); 13C NMR (CDCl3, 62.9
MHz) ꢀ 18.61, 32.45, 56.85, 65.70, 126.95, 135.72, 167.40.
2-Bromo-3-chloropropyl Methacrylate (19):
1H NMR
(CDCl3, 250 MHz) ꢀ 1.97 (s, 3H), 3.79–3.91 (m, 2H), 4.30–
4.36 (m, 1H), 4.47–4.56 (m, 2H), 5.64 (s, 1H), 6.17 (s, 1H);
13C NMR (CDCl3, 62.9 MHz) ꢀ 18.25, 44.72, 47.34, 64.58,
126.60, 135.61, 167.43; Mass spectra m=e: 242 (M þ 2, 0.4%),
205 (M ꢁ Cl, 0.9%), 161 (M ꢁ Br, 2.7%), 155 (M ꢁ
CH2=C(CH3)CO2, 5.5%), 85 (M ꢁ CH2CHBrCH2Cl, 16.6%).
3-Chloro-2-hydroxypropyl Methacrylate (8):
1H NMR
(CDCl3, 250 MHz) ꢀ 1.96 (s, 3H), 2.94 (s, 1H), 3.57–3.71 (m,
2H), 4.09–4.17 (m, 1H), 4.28–4.31 (d, 2H, J ¼ 7 Hz), 5.62 (s,
1H), 6.15 (s, 1H); 13C NMR (CDCl3, 62.9 MHz) ꢀ 18.29, 46.02,
65.48, 69.65, 126.55, 135.72, 167.44; Mass spectra m=e: 178
(M, 0.9%), 143 (M ꢁ Cl, 1.2%).
1-Chloro-2-iodocyclohexane (20):
1H NMR (CDCl3, 250
2-Hydroxy-3-iodopropyl Methacrylate (9):
1H NMR
MHz) ꢀ 1.47–1.54 (m, 2H), 1.70–1.96 (m, 4H), 2.17–2.30 (m,
2H), 3.82 (s, 1H), 4.66 (s, 1H); 13C NMR (CDCl3, 62.9 MHz) ꢀ
22.59, 23.09, 25.20, 34.45, 35.33, 64.25; Mass spectra m=e: 246
(M þ 2, 3.7%), 244 (M, 10.3%), 117 (M ꢁ I, 13.4%).
(CDCl3, 250 MHz) ꢀ 1.96 (s, 3H), 2.73 (s, 1H), 3.24–3.39 (m,
2H), 3.90–3.92 (m, 1H), 4.27–4.29 (m, 2H), 5.63 (s, 1H), 6.15
(s, 1H); 13C NMR (CDCl3, 62.9 MHz) ꢀ 9.02, 18.35, 67.23,
69.35, 126.59, 135.72, 167.37.
1,2-Dibromo-3-phenoxypropane (10): 1H NMR (CDCl3, 250
MHz) ꢀ 3.78–3.91 (m, 2H), 4.31–4.43 (m, 3H), 6.91–7.01 (m,
3H), 7.21–7.32 (m, 2H); 13C NMR (CDCl3, 62.9 MHz) ꢀ 31.74,
46.71, 68.0, 113.81, 120.63, 128.57, 156.91; Mass spectra m=e:
296 (M þ 4, 16.2%), 294 (M þ 2, 41.7%), 292 (M, 14.1%),
203 (M þ 4 ꢁ PhO, 3.2%), 201 (M þ 2 ꢁ PhO, 8.7%), 199 (M
ꢁ PhO, 5.3%).
We acknowledge the support of this work by Shiraz Univer-
sity Research Council and Iran TWAS Chapter Based at
ISMO.
References
1 C. H. Behrens, S. Y. Ko, K. B. Sharpless, and F. J. Walker,
J. Org. Chem., 50, 5687 (1985).
1,2-Dichloro-3-phenoxypropane (11): 1H NMR (CDCl3, 250
MHz) ꢀ 3.86–4.00 (m, 2H), 4.26–4.41 (m, 3H), 6.91–7.02 (m,
3H), 7.24–7.33 (m, 2H); 13C NMR (CDCl3, 62.9 MHz) ꢀ 45.02,
57.30, 68.09, 114.72, 121.66, 129.62, 157.94.
2
3
W. A. Nugent, J. Am. Chem. Soc., 114, 2768 (1992).
M. Tokunaga, J. F. Larrow, F. Kakiuchi, and E. N.
Jacobsen, Science, 227, 936 (1997).
1,2-Dibromo-1-phenylethane (12): 1H NMR (CDCl3, 250
MHz) ꢀ 4.01–4.11 (m, 2H), 5.11–5.17 (dd, 1H, J ¼ 10, 5 Hz),
7.35–7.39 (br, s, 5H); 13C NMR (CDCl3, 62.9 MHz) ꢀ 35.00,
50.86, 127.64, 128.85, 129.17, 138.6; Mass spectra m=e: 266 (M
þ 4, 0.4%), 264 (M þ 2, 0.5%), 262 (M, 0.4%), 185 (M þ 4 ꢁ
Br, 1.3%), 183 (M ꢁ Br, 1.2%).
4
5
6
C. R. Bonini and G. Righi, Synthesis, 1994, 225.
J. G. Smith, Synthesis, 1984, 629.
J. Yamada, M. Yumoto, and Y. Yamamoto, Tetrahedron
Lett., 30, 4255 (1989).
7
J. Org. Chem., 54, 4966 (1989).
J. P. Konopelski, M. A. Boehler, and T. M. Tarasow,
1,2-Dibromo-3-isopropyloxypropane (13):
1H NMR
8
9
E. J. Corey and J. Das, Tetrahedron Lett., 23, 4217 (1982).
Y. Ueda and S. C. Maynard, Tetrahedron Lett., 29, 5197
(CDCl3, 250 MHz) ꢀ 1.17–1.20 (m, 6H), 3.64–3.87 (m, 5H),
4.20–4.25 (m, 1H); 13C NMR (CDCl3, 62.9 MHz) ꢀ 22.04,
33.48, 49.78, 68.63, 72.62.
(1988).
10 H. R. Nace and G. A. Crosby, J. Org. Chem., 44, 3105

N. Iranpoor et al.
Bull. Chem. Soc. Jpn., 77, No. 10 (2004) 1891
(1979).
3869 (1972).
23 P. E. Sonnet and J. E. Oliver, J. Org. Chem., 41, 3279
(1976).
24 R. C. Cambie, W. I. Noall, G. J. Potter, P. S. Rutledge, and
P. D. Woodgate, J. Chem. Soc., Perkin Trans. 1, 1977, 226.
25 J. Barluenga, J. M. Gonzalez, P. J. Campos, and G.
Asensio, Angew. Chem., Int. Ed. Engl., 24, 319 (1985).
26 C. H. Robinson, L. Finckenor, E. P. Oliveto, and D. Gould,
J. Am. Chem. Soc., 81, 2191 (1959).
11 A. J. Sisti and A. C. Vitale, J. Org. Chem., 37, 4090 (1972).
12 C. A. Stewart and C. A. Vanderwerf, J. Am. Chem. Soc.,
76, 1259 (1954).
13 Y.-G. Suh, B. A. Koo, J.-A. Ko, and Y.-S. Cho, Chem.
Lett., 1993, 1907.
14 N. Iranpoor, F. Kazemi, and P. Salehi, Synth. Commun.,
27, 1247 (1997).
15 C. E. Garrett and G. C. Fu, J. Org. Chem., 62, 4534 (1997).
16 H. Kotsuki, T. Shimanouchi, R. Ohshima, and S. Fujiwara,
Tetrahedron, 54, 2709 (1998).
27 N. Iranpoor, H. Firouzabadi, G. Aghapour and A. R.
Vaezzadeh, Tetrahedron, 58, 8689 (2002).
17 H. Sharghi and H. Naeimi, Synlett, 1998, 1343.
18 N. Iranpoor and H. Adibi, Bull. Chem. Soc. Jpn., 73, 675
(2000).
19 D. Diaz, T. Martin, and V. S. Martin, J. Org. Chem., 66,
7231 (2001).
20 H. Sharghi and M. M. Eskandari, Synthesis, 2002, 1519.
21 H. Sharghi, A. R. Massah, H. Eshghi, and K. Niknam,
J. Org. Chem., 63, 1455 (1998).
28 a) D. R. Dalton, J. B. Henderickson, and D. Jones, Chem.
Commun., 1966, 591. b) R. E. Buckles and J. W. Long, J. Am.
Chem. Soc., 73, 998 (1951). c) E. Baciocchi and R. Ruzziconi,
J. Org. Chem., 49, 3395 (1984). d) M. Mousseron and F.
Winternitz, Compt. Rend., 219, 132 (1944). e) M. Mousseron,
R. Jacquier, R. Henry, and M. Mousseron-Canet, Bull. Soc. Chim.
Fr., 1953, 628.
29 Z. Paryzek and R. Wydra, Tetrahedron Lett., 25, 2601
(1984).
22 N. S. Isaacs and D. Kirkpatrick, Tetrahedron Lett., 13,