Facile synthesis of E-diiodoalkenes: H2O2-activated reaction of alkynes with iodine

Article abstract of DOI:10.1080/00397910701545171

Hydrogen peroxide was found to activate iodine in the addition reaction with triple bonds. A facile and technologically straightforward procedure was developed for the synthesis of E-diiodoalkenes based on the reaction of alkynes with an I2-H2O2 system in

Full text of DOI:10.1080/00397910701545171

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Facile Synthesis of E‐Diiodoalkenes:
H O ‐Activated Reaction of Alkynes with
2
2
Iodine
a
a
a
Alexander O. Terent'ev , Dmitry A. Borisov , Igor B. Krylov & Gennady I.
a
Nikishin
a
N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of
Sciences, Moscow, Russia
Version of record first published: 10 Sep 2007.
To cite this article: Alexander O. Terent'ev , Dmitry A. Borisov , Igor B. Krylov & Gennady I. Nikishin
(
2007): Facile Synthesis of E‐Diiodoalkenes: H O ‐Activated Reaction of Alkynes with Iodine, Synthetic
2 2
Communications: An International Journal for Rapid Communication of Synthetic Organic Chemistry, 37:18,
151-3164
3
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w
Synthetic Communications , 37: 3151–3164, 2007
Copyright # Taylor & Francis Group, LLC
ISSN 0039-7911 print/1532-2432 online
DOI: 10.1080/00397910701545171
Facile Synthesis of E-Diiodoalkenes: H O -
2
2
Activated Reaction of Alkynes with Iodine
Alexander O. Terent’ev, Dmitry A. Borisov, Igor B. Krylov,
and Gennady I. Nikishin
N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of
Sciences, Moscow, Russia
Abstract: Hydrogen peroxide was found to activate iodine in the addition reaction with
triple bonds. A facile and technologically straightforward procedure was developed for
the synthesis of E-diiodoalkenes based on the reaction of alkynes with an I –H O
2 2
2
system in THF. Selective iodination of terminal and internal alkynes containing
electron-donating and electron-withdrawing substituents afforded 16 E-diiodoalkenes
in yields up to 89%.
Keywords: alkynes, E-diiodoalkenes, hydrogen peroxide, iodination
INTRODUCTION
In the past decades, iodoalkenes have attracted considerable attention because
these compounds serve as key reagents in metal-complex-catalyzed
[
1–7]
reactions.
cedures for the synthesis of these compounds. Nowadays, there are
Interest in iodides has stimulated the development of pro-
[8–38]
numerous efficient methods for the preparation of iodoalkenes
[
iodoarenes,
and
which are similar to the former compounds in application
39–48]
and mechanism of synthesis. The mechanism of most methods for iodination
is based on the generation of iodine-containing species with a particular
electrophilicity.
Received in the U.K. October 20, 2006
Address correspondence to Alexander O. Terent’ev, N. D. Zelinsky Institute of
Organic Chemistry, Russian Academy of Sciences, 119991 Leninsky Prospect 47,
Moscow, Russia. E-mail: terentev@ioc.ac.ru
3
151

3
152
A. O. Terent’ev et al.
In the present study, we developed a new approach to the synthesis of
vicinal E-diiodoalkenes. The preparation of the latter compounds has been
[
26–35]
the subject of much investigation.
performed with the use of iodine in CHCl or chlorobenzene,
Iodination of alkynes was first
[
26,27]
as well
This method was examined in sufficient detail in a
where the target products were prepared in high yields (NMR spec-
3
[
28]
as in MeOH.
[
27]
study,
troscopic data). However, more recently it has been demonstrated that
this reaction proceeds at a low rate and is characterized by a low conversion
of alkynes. To remedy these flaws, the CuI–I system in CH CN was
2
3
[
29]
employed.
of the following reagents: I –Al O system,
In other methods, iodination was performed with the use
[
30,31]
ICl followed by the reaction
bis(pyridine)iodonium(I) tetrafluoroborate in the presence
2
2 3
[
32]
with NaI,
of an iodide donor,
Z-diiodoalkenes were also synthesized by iodination of organometallic
[
33,34]
[35]
and KMnO –HI system in CH CN.
Vicinal
4
3
[
36–38]
compounds.
In the present study, we used the simple, convenient, and technologically
straightforward I –H O system as the iodinating agent. This system has
2
2 2
[49]
already found use in the synthesis of methoxy- and hydroxyiodoalkanes,
[
40,50]
[51]
[52]
iodoarenes,
geminal bishydroperoxides,
and iodoketones.
RESULTS AND DISCUSSION
We used the H O -I system for iodination of terminal alkynes 1a, 1f–j, 1l,
2
2 2
1n, and 1p and internal alkynes 1b–e, 1k, 1m, and 1o containing electron-
donating and electron-withdrawing substituents. The products of this
reaction, E-diiodoalkenes 2a–p, were isolated in yields up to 89%
(
Scheme 1, Table 1).
The reactions were carried out by the successive addition of a 37%
aqueous H O solution and iodine to a solution of alkyne in THF in two
2
2
different temperature conditions: at 58–628C (procedure A) and 20–258C
procedure B).
We used tetrahydrofuran as the solvent because it makes it possible to
(
perform homogenization of the reaction mixture, has the boiling point at
which homolytic O-O bond cleavage in H O does not initiate radical
2
2
Scheme 1. Synthesis of E-diiodoalkenes 2a–p by iodination of alkynes with the
I –H O system.
2
2 2

a
Table 1. Synthesis of E-diiodoalkenes 2a–p by the reaction of alkynes 1a–p with the I
b
20–258C )
2
–H
2
O
2
system at different temperatures (58–628C and
Procedure A (58–628C)
Procedure B (20–258C)
c
Yield 2a–p, (%)
c
Yield 2a–p, (%)
E-Diiodoalkene, 2a–p
Molar ratio I /1a–p
2
Time (h)
Time (h)
1
1
74
52
10
76
44
d
d
1
12
1
1
83
56
10
4
89
72
60
79
56
88
d
1
d
4
d
2
4
e
4
1
1
1
1.5
1
85
84
10
12
15
89
1.5
88
69
68
86
68
86
75
d
d
1
.5
.5
15
15
e
f
1
g
1
5
(continued)

Table 1. Continued
E-Diiodoalkene, 2a–p
Procedure A (58–628C)
Procedure B (20–258C)
c
Yield 2a–p, (%)
c
Yield 2a–p, (%)
Molar ratio I /1a–p
2
Time (h)
Time (h)
1
0.5
78
40
20
85
49
1
1
1
1
1
1
8
1.5
70
61
20
75
62
d
.5
d
20
1
1.5
1.5
1.5
53
70
82
15
59
70
88
15
15

1
1
1.5
1.5
4
48
11
15
20
24
62
44
1
.5
.5
68
46
73
26
d
d
1
4
48
1
4
2
75
41
24
72
45
1
.5
24
a
Reaction conditions (procedure A): alkyne (0.3 g) was dissolved in THF (5 ml), and 37% aq H O soln. (5 mmol/1 mmol of alkyne) and then I
2
2
2
2
(
(
1 mmol/1 mmol of alkyne) were added at room temperature. The reaction mixture was heated at 58–628C (moderate refluxing) for 0.5–4 h.
b
2 2
Reaction conditions (procedure B): alkyne (0.3 g) was dissolved in THF (5 ml), and 37% aq. H O soln (5 mmol/1 mmol of alkyne) and then I
1 mmol/1 mmol of alkyne) were added at room temperature. The resulting mixture was kept at 20–258C for 8–24 h.
The yields are given with respect to the isolated product.
c
d
2 2
Reactions were carried out in the absence of H O .
e
f
2 2
Reaction with use of 0.5 ml of water (without H O ).
Tenfold molar excess of H O with respect to alkyne.
2
2
g
Equimolar amount of H
2
O
2
with respect to alkyne.

3
156
A. O. Terent’ev et al.
reactions as side processes, is easily separated from the reaction products, and
[
51,53]
unlike alcohols, for example,
is not oxidized with iodine.
All experiments were carried out with the use of an equimolar amount of
iodine (except in the synthesis of 2n and 2p, one-and-a-half-fold excess of
iodine was used) and a fivefold molar excess of H O with respect to alkynes.
2
2
The activating effect of H O in the addition reaction of iodine at the
2
2
triple bond is exemplified by iodination of alkynes 1a, 1b, 1e, 1h, and 1n.
According to the procedure A (58–628C), diiodoalkene 2a was synthesized
in 74% yield (the reaction time was 1 h). Under the same conditions but in
the absence of H O , the yield decreased to 52%. The yield of diiodoalkene
2
2
2a prepared according to the procedure B (20–258C) was 76% (after 10 h);
in the absence of H O , the yield was lower (44%). An analogous difference
in the synthesis of diiodoalkenes 2b, 2e, and 2h was observed when the cor-
responding alkynes were iodinated in the presence or absence of H O . Iodina-
2
2
2
2
tion of compound 1n containing an electron-withdrawing substituent without
the involvement of H O afforded diodoalkene 2n in a yield of 26% (reaction
time was 48 h). The use of H O made it possible to increase the yield of 2n to
2
2
2
2
73% (reaction time was 24 h). The influence of the amount of H O on the
2 2
yield of diiodoalkene 2e was exemplified by iodination of alkyne 1e. The
maximum yield (86%) was achieved with the use of a five- or tenfold molar
excess of hydrogen peroxide; with an equimolar amount, the yield was
75%; in the absence of H O , the yield was only 68%. Water that is present
in an H O solution has no activating effect on iodination of alkynes. This con-
2 2
2
2
clusion is evident from a comparison of the results of the reaction of alkyne 1b
with iodine in THF with the addition of water and in the absence of H O (the
2
2
yield of 2b was 56%) and iodination with the use of a H O solution (the yield
2
2
was higher at 72%).
The temperature of the reaction plays an important role in iodination with
the involvement of hydrogen peroxide. At 20–258C (procedure B), all alkynes
1
o–p, including those containing electron-withdrawing groups, are selec-
tively iodinated to give the target products in moderate (44–49%) to high
82–89%) yields. After the treatment of the reaction mixture and before chro-
(
matographic purification (see the Experimental section), the purity of
compounds 2b–e and 2j–2 m was about 95%. Diiodoalkenes prepared
according to procedure B were purified by simple flash chromatography. Iodi-
nation at 58–628C (procedure A) allows one to decrease the reaction time to
0.5–4 h. The synthesis of diiodoalkenes 2a–f according to procedure A is as
selective as that performed according to procedure B. Alcohols 2i–m were
produced in lower yields, apparently a result of partial oxidation. The selectiv-
ity of the synthesis of diiodoalkenes decreases with increasing reaction temp-
erature, which can be observed in NMR spectra showing the presence of
impurities in the crude reaction products prepared according to procedure A.
The E isomerism was assumed for all diiodoalkenes presented in Table 1.
The stereochemistry of the known compounds was determined based on the
correspondence with the NMR spectra and the melting points published in

E-Diiodoalkenes
3157
Scheme 2. Possible mechanism of iodination of alkynes with the I –H O system.
2 2 2
the literature. The structures of the new compounds were assumed by analogy
based on the identity of the iodination mechanism.
Activation of iodination with H O is apparently attributed to oxidation of
2
2
þ
I and the initial generation of an “I ”-containing electrophilic species. The
2
next step occurs with the involvement of alkyne and affords a cyclic inter-
[
33]
mediate,
Scheme 2).
Therefore, hydrogen peroxide acts as a mild activator of the addition of
which is attacked by the iodine donor to form an E-diiodoalkene
(
iodine to the triple bond, and it does not virtually oxidize the double and
triple bonds or iodine, in diiodoalkenes.
CONCLUSIONS
The convenient and technologically simple I –H O system was used for the
2 2
2
first time for the preparation of E-diiodoalkenes from alkynes in satisfactory
yields. This method allows one to perform selective iodination of terminal
and internal alkynes containing electron-donating and electron-withdrawing
substituents. Iodination can be performed in two temperature conditions. At
2
0–258C, the selective formation of E-diiodoalkenes is completed over 8–
4 h. At 58–628C, the reaction time decreases to 0.5–4 h but the selectivity
is somewhat lower. In most cases, E-diiodoalkenes can be simply purified
2
by flash chromatography.
EXPERIMENTAL
1
NMR spectra were recorded on Bruker AC-200 (200.13 MHz for H and
1
3
0.32 MHz for C), Bruker WM-250 (250.13 MHz for H and 62.9 MHz
1
5
1
3
1
13
for C), and Bruker AN-300 (300.13 MHz for H and 75.4 MHz for C)
instruments in CDCl3 solutions. Analytical thin-layer chromatography
(TLC) used Silufol UV-254, Silpearl as the sorbent and starch as the binder.

3
158
A. O. Terent’ev et al.
Flash chromatography was performed on silica gel (63–200 mesh, Merk).
Alkynes and Na S O were purchased from Acros. Tetrahydrofuran, iodine,
and a 37% aqueous H O solution (all reagent grade) were used without
2
2 5
2
2
additional purification.
General Procedure for Synthesis of E-diiodoalkene (2a–p).
Procedure A
Alkyne 1a–p (0.3 g) was dissolved in THF (5 ml), a 37% aqueous H O2
2
solution (5 mmol/1 mmol of alkyne) was added at 20–258C, and I2
(
1 mmol/1 mmol of alkyne) was added with stirring. The reaction mixture
was heated at 58–628C for 0.5–4 h and then cooled to room temperature.
Procedure B
Alkyne 1a–p (0.3 g) was dissolved in THF (5 ml), a 37% aqueous H O2
2
solution (5 mmol/1 mmol of alkyne) was added at 20–258C, and I2
(1 mmol/1 mmol of alkyne) was added with stirring. The reaction mixture
was kept for 8–24 h.
General Procedure for Isolation of E-diiodoalkenes (2a–p)
Hexane (30 ml) or Et O (40 ml) (for isolation of polar compounds 2i–2 m and
2
2p) and H O (20 ml) were added. The lower aqueous layer was separated. The
upper organic layer was washed with a 5% Na S O solution until the layer
2
2
2 5
became colorless and then with H O (4 ꢀ 5 ml), dried under MgSO , filtered,
2
4
and concentrated. The residue was purified by silica-gel flash chromatography.
Diiodoalkenes 2h–l and 2n–p synthesized according to the procedure B were
purified by silica-gel column chromatography. An ethyl acetate-hexane
mixture (percentage of ethyl acetate 0–20%) was used as the eluent.
Influence of Experimental Conditions on Iodination of Alkynes
The synthesis and isolation of E-diiodoalkenes were performed analogously in
the following reactions: in the absence of H O , with the use of an equimolar
2
2
and tenfold molar excess of H O with respect to alkyne, and in the synthesis
2
2
of diiodoalkenes 2n using a 1.5-fold molar excess of iodine with respect to
alkyne.
The synthesis of diiodoalkene 2b by the reaction with the addition of
water (without H O ) was carried out using 0.5 ml of water; the synthesis
and isolation were performed as described previously.
2
2

E-Diiodoalkenes
Data
3159
[
54]
(
1E)-1,2-Diiodo-1-heptene (2a): Pale yellow oil. Rf ¼ 0.94 (TLC, hexane);
1
H NMR (250.13 MHz, CDCl ): d ¼ 0.93 (t, 3H, CH , J ¼ 7.2 Hz), 1.25–1.65
3 3
1
3
(
m, 6H, CH ), 2.52 (t, 2H, CH CI, J ¼ 7.2 Hz), 6.82 (s, 1H, CH); C NMR
2
2
(
62.9 MHz, CDCl ): d ¼ 14.1 (CH ), 22.6, 27.9, 30.4 (CH ), 44.7 (CH CI),
3 3 2 2
þ
9.1 (CHI), 104.5 (CI); MS (EI, 70 eV), m/z [I (%)]: 350 [M] (19), 279
rel
7
þ
þ
[M-C H ] (1), 127 [I] (21).
5
11
(
2E)-2,3-Diiodo-2-pentene (2b): Pale yellow oil. Rf ¼ 0.93 (TLC, hexane);
1
H NMR (300.13 MHz, CDCl ): d ¼ 1.05 (t, 3H, CH , J ¼ 7.4 Hz), 2.59
3
3
1
3
(
s, 3H, CH CI), 2.68 (q, 2H, CH , J ¼ 7.4 Hz); C NMR (75.47 MHz,
3
2
CDCl ): d ¼ 12.9 (CH CH ), 40.3, 45.1 (CH CI, CH CI), 92.3, 104.3 (CI);
3 3 2 2 3
þ
þ
þ
MS (EI, 70 eV), m/z [I (%)]: 322 [M] (43), 195 [M-I] (100), 127 [I]
rel
þ
(27), 67 [M-HI-I] (87). Anal. calcd, for C H I : C, 18.65; H, 2.50; I,
5
8 2
7
8.84. Found: C, 18.45; H, 2.39; I, 78.98.
1
(
2E)-2,3-Diiodo-2-hexene (2c): Pale yellow oil. Rf ¼ 0.90 (TLC, hexane); H
NMR (250.13 MHz, CDCl ): d ¼ 0.95 (t, 3H, CH , J ¼ 7.6 Hz), 1.58 (m, 2H,
3
3
1
3
CH ), 2.59–2.69 (m, 5H, CH , CH ); C NMR (62.9 MHz, CDCl ): d ¼ 12.9
2
2
3
3
(
(
CH CH ), 21.7 (CH CH ), 40.4 (CH ), 52.4 (CH CI), 93.2, 102.9 (CI); MS
2 3 2 3 3 2
þ
þ
þ
EI, 70 eV), m/z [Irel (%)]: 322 [M] (43), 195 [M-I] (100), 127 [I] (27).
Anal. calcd. for C H I : C, 21.45; H, 3.00; I, 75.55. Found: C, 21.65; H,
6
10 2
2
.89; I, 75.87.
[
22]
(
3E)-3,4-Diiodo-3-hexene (2d): Pale yellow oil. Rf ¼ 0.83 (TLC, hexane);
1
H NMR (200.13 MHz, CDCl ): d ¼ 1.03 (t, 6H, CH , J ¼ 7.3 Hz), 2.68
3
3
1
3
(
q, 4H, CH , J ¼ 7.3 Hz); C NMR (50.32 MHz, CDCl ): d ¼ 12.8 (CH ),
2
3
3
4
5.1 (CH ), 102.6 (CI).
2
[
55]
(
4E)-4,5-Diiodo-4-octene (2e):
Pale yellow oil. Rf ¼ 0.98 (TLC, hexane);
1
H NMR (250.13 MHz, CDCl ): d ¼ 0.96 (t, 6H, CH , J ¼ 7.6 Hz), 1.59
3
3
1
3
(
m, 4H, CH ), 2.68 (t, 4H, CH , J ¼ 7.6 Hz); C NMR (62.9 MHz, CDCl ):
2
2
3
d ¼ 12.8 (CH ), 21.6, 52.6 (CH ), 102.0 (CI); MS (EI, 70 eV), m/z [I
3
þ
2
rel
þ
þ
þ
(
%)]: 364 [M] (12), 127 [I] (7), 109 [M-I-HI] (82), 67 [M-2I-Pr] (100).
[
54]
[
(E)-1,2-Diiodovinyl]benzene (2f):
[
White crystals. Mp ¼ 73–748C (Mp¼
54]
1
7
4–768C):
; Rf ¼ 0.6 (TLC, hexane); H NMR (200.13 MHz, CDCl ):
3
1
3
d ¼ 7.25 (s, 1H, CH), 7.30–7.40 [br.s, 5H, CH(Ar)];
C NMR
(
50.32 MHz, CDCl ): d ¼ 80.9 (CHI), 96.3 (CI), 128.4, 128.5, 128.9
3
[
CH(Ar)], 143.0 [C(Ar)].
[
27]
(
1E)-3-Bromo-1,2-diiodo-1-propen (2g): Pale yellow oil. Rf ¼ 0.28 (TLC,
1
hexane); H NMR (250.13 MHz, CDCl ): d ¼ 4.35 (s, 2H, CH ), 7.16 (s, 1H,
3
2
1
3
CH); C NMR (62.9 MHz, CDCl ): d ¼ 42.7 (CH ), 85.8 (CH), 96.3 (C).
3
2

3
160
A. O. Terent’ev et al.
(
1E)-1,2-Diiodo-3-methoxy-1-propen (2h): Pale yellow oil. Rf ¼ 0.21 (TLC,
1
hexane); H NMR (250.13 MHz, CDCl ): d ¼ 3.35 (s, 3H, CH ), 4.13 (s, 2H,
3
3
1
3
CH ), 7.15 (s, 1H, CH); C NMR (62.9 MHz, CDCl ): d ¼ 57.6 (OCH ), 78.7
2
3
3
þ
(
[
(
CH ), 81.7, 100.8 (CI); MS (EI, 70 eV), m/z [I (%)]: 324 [M] (20), 293
2
rel
þ
þ
þ
þ
þ
M-OMe] (3), 254 [I2] (2), 197 [M-I] (61), 141 [ICH2] (28), 127 [I]
32), 39 [M-2I-CH OMe] (100).
þ
2
[30]
2E)-2,3-Diiodo-2-propen-1-ol (2i):
(
Pale yellow oil. Rf ¼ 0.39 (TLC,
1
hexane–ethyl acetate ¼ 4:1); H NMR (300.13 MHz, CDCl ): d ¼ 3.25–
3
1
3
.40 (br. s, 1H, OH), 4.22 (s, 2H, CH ), 7.02 (s, 1H, CH); C NMR
3
2
(
75.47 MHz, CDCl ): d ¼ 70.3 (CH ), 80.0, 104.3 (C, CH); MS (EI, 70
þ þ þ
rel 2
þ þ þ
M-I] (100), 153 [M-I-CH OH] (23), 127 [I] (51).
2
3
2
eV), m/z [I (%)]: 310 [M] (18), 293 [M-OH] (2), 254 [I ] (9), 197
[
(
3E)-3,4-Diiodo-3-buten-2-ol (2j): Colorless oil. Rf ¼ 0.31 (TLC, hexane–
1
ethyl acetate ¼ 10:1); H NMR (250.13 MHz, CDCl ): d ¼ 1.20 (d, 3H,
3
CH CH, J ¼ 6.2 Hz), 2.45–2.60 (br.s, 1H, OH), 4.12 (q, 1H, CHOH,
3
1
3
J ¼ 6.2 Hz), 6.94 (m, 1H, CHCI); C NMR (62.9 MHz, CDCl ): d ¼ 22.2
3
(
C, 14.83; H, 1.87; I, 78.36. Found: C, 14.67; H, 1.81; I, 78.64.
CH CH), 72.7, 77.4 (CHOH, CHI), 113.9 (CI). Anal. calcd. for C H I O:
3 4 6 2
[
56]
(
(
(
(
3E)-3,4-Diiodo-3-hexen-2-ol (2k) : Colorless crystals. Mp ¼ 70.5–71.58C
1
Et O). Rf ¼ 0.43 (TLC, hexane–ethyl acetate ¼ 10:1);
H
NMR
2
300.13 MHz, CDCl ): d ¼ 1.03 (t, 3H, CH CH , J ¼ 7.35 Hz), 1.19
3
3
2
d, 3H, CH CH, J ¼ 6.2 Hz), 2.15–2.29 (br.s, 1H, OH), 2.71–2.83 (m, 2H,
3
1
3
CH CI), 4.25 (q, 1H, CHCI, J ¼ 6.2 Hz); C NMR (75.47 MHz, CDCl ):
2
3
d ¼ 12.3 (CH CH ), 22.6 (CH CH), 44.7 (CH ), 77.4 (CH), 101.6, 111.8
3
2
3
2
þ þ
CI); MS (EI, 70 eV), m/z [I (%)]: 352 [M] (100), 337 [M-CH ] (11),
rel 3
(
þ
þ
þ
þ
2
25 [M-I] (71), 207 [M-I-H O] (67), 181 [M-I-CH CHO] (38), 127 [I]
3
2
þ
(
34), 98 [M-2I] (52).
[
35]
(
3E)-3,4-Diiodo-2-methyl-3-butene-2-ol (2l):
Pale yellow crystals.
Rf ¼ 0.47 (TLC, hexane–ethyl
[35]
Mp ¼ 55.5–578C (Et O) (Mp ¼ 518C);
2
1
acetate ¼ 10:1); H NMR (250 MHz, CDCl ): d ¼ 1.59 (s, 6H, CH ), 2.50–
3
1
3
3
.60 (br.s, 1H, OH), 7.17 (s, 1H, CH); C NMR (62.9 MHz, CDCl ):
2
3
d ¼ 29.6 (CH ), 72.3, 75.8 (CI, COH), 114.4 (CI); MS (EI, 70 eV), m/z
3
þ
þ
þ
2
[
(
[
I
(%)]: 338 [M] (31), 323 [M-Me] (45), 278 [M-H O-CH CHCH ]
2
rel
3
þ
þ
þ
þ
4), 254 [I2] (12), 211 [M-I] (36), 195 [M-IO] (38), 127 [I] (50), 43
CH CHCH ] (100).
þ
3
3
(
3E)-3,4-Diiodo-3-hexene-1-ol (2m): Colorless crystals. Mp ¼ 48.5–508C.
1
Rf ¼ 0.30 (TLC, hexane–ethyl acetate ¼ 10:1); H NMR (300.13 MHz,
CDCl ): d ¼ 1.05 (t, 3H, CH CH , J ¼ 7.4 Hz), 1.60-1.70 (br.s, 1H, OH),
3
3
2
2
3
.73 (q, 2H, CH CH , J ¼ 7.4 Hz), 2.99 (t, 2H, CH CH OH, J ¼ 6.6 Hz),
2 3
2
3
2
2
1
3
.82 (t, 2H, CH O, J ¼ 6.6 Hz); C NMR (75.47 MHz, CDCl ): d ¼ 10.6

E-Diiodoalkenes
3161
(
CH CH ), 45.4, 53.2 (CH CI), 60.8 (CH OH), 95.4, 106.2 (CI); MS (EI, 70
3
2
2
2
þ
þ
þ
eV), m/z [I (%)]: 352 [M] (19), 225 [M-I] (89), 195 [M-I-CH O] (48),
1
rel
2
þ þ
27 [I] (13), 67 [M-2I-CH OH] (100).
2
[
57]
Methyl (2E)-2,3-diiodoacrylate (2n): Pale yellow crystals. Mp ¼ 37–388C
[
57]
1
(
Mp¼ 37.5–38.58C);
Rf ¼ 0.57 (TLC, hexane–ethyl acetate ¼ 10:1); H
1
3
NMR (250.13 MHz, CDCl ): d ¼ 3.84 (s, 3H, CH ), 7.75 (s, 1H, CH);
C
3
3
NMR (62.9 MHz, CDCl ): d ¼ 53.3 (OCH ), 85.5 (CI), 87.6 (CH), 164.0
3
3
þ þ
C 55 O); MS (EI, 70 eV), m/z [I (%)]: 338 [M] (74), 307 [M-OMe]
rel
(
(
þ
þ
þ
20), 278 [M-HCOOMe] (35), 254 [I ] (81), 211 [M-I] (69), 179 [M-I-
2
þ
þ
þ
MeOH] (87), 151 [M-I-HCO Me] (28), 127 [I] (100).
2
[
58]
Dimethyl (2E)-2,3-diiodo-2-butendioate (2o):
[
Pale yellow crystals.
Rf ¼ 0.43 (TLC, hexane–ethyl
58]
Mp ¼ 122–1248C (Mp¼ 1258C);
1
13
acetate ¼ 5:1); H NMR (250.13 MHz, CDCl ): d ¼ 3.88 (s, 6H, CH );
C
3
3
NMR (62.9 MHz, CDCl ): d ¼ 53.7 (OCH ), 88.1 (CI), 165.2 (C 55 O); MS
3
3
þ
þ
(
EI, 70 eV), m/z [I (%)]: 396 [M] (27), 365 [M-OMe] (12), 337 [M-
rel
þ
þ
þ
þ
COOMe] (3), 254 [I2] (30), 269 [M-I] (5), 179 [M-I-MeOH-COOMe]
þ þ þ
68), 151 [M-I-2HCO Me] (28), 127 [I] (17), 59 [COOMe] (100).
2
(
[
59]
(
2E)-2,3-Diiodoacrylic acid (2p):
01.58C (Mp ¼ 103.3–104.58C);
Pale yellow crystals. Mp ¼ 100.0–
Rf ¼ 0.29 (TLC, hexane–ethyl
[
59]
1
1
acetate ¼ 4:1); H NMR (300.13 MHz, CDCl ): d ¼ 8.03 (s, 1H, CH),
3
1
3
9
.75–9.85 (br.s, 1H, OH); C NMR (75.47 MHz, CDCl ): d ¼ 85.4, 90.8
3
þ
(
[
CH ), 168.4 (COOH); MS (EI, 70 eV), m/z [I (%)]: 324 [M] (88), 254
2
þ
rel
þ
þ
þ
I ] (46), 197 [M-I] (87), 153 [M-I-CO ] (87), 127 [I] (100).
2
2
ACKNOWLEDGMENTS
This work is supported by the Program for Support of Leading Scientific
Schools of the Russian Federation (Grant NSh 5022.2006.3), the Grant of
President of Russian Federation (No. MK-3515. 2007. 3), the Russian Foun-
dation for Basic Research (Grant No. 07-03-00338), and the Russian
Science Support Foundation.
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