Iodoalkoxylation, iodohydroxylation, and iodoacetoxylation of alkenes catalyzed by CdCl2·2.5H2O

Full text of DOI:10.1134/S1070428008070233

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2008, Vol. 44, No. 7, pp. 1082−1083. © Pleiades Publishing, Ltd., 2008.
Original Russian Text © V.Z. Mekhtieva, S.F. Karaev, 2008, published in Zhurnal Organicheskoi Khimii, 2008, Vol. 44, No. 7, pp. 1091−1092.
SHORT
COMMUNICATIONS
Iodoalkoxylation, Iodohydroxylation, and Iodoacetoxylation
of Alkenes Catalyzed by CdCl2 · 2.5H2O
V. Z. Mekhtieva and S. F. Karaev
Azerbaidzhan State Petroleum Academy, Baku, Az1010 Azerbaidzhan
e-mail: veneramz@rambler.ru
Received July 24, 2007
DOI: 10.1134/S1070428008070233
Reactions of alkenes with iodine in alcohol, water, or
carboxylic acid in the presence of catalysts {Cu(OAc)2
[1], Ce(SO3CF3)4 [2], ZnCl2 [3], or iodosobenzene
dichloride [4]} provide a convenient procedure for
preparation of iodoethers, iodohydrins,and iodoacetates.
solution, and extracted with ether. Ether was removed,
the residue was distilled in a vacuum. Yield 52.7 g (80%),
bp 114–115°C (1 mm Hg), d420 1.5218, nD20 1.5503 {yield
62%, bp 115°C (1 mm Hg), d420 1.5215, nD20 1.5500 [6]}.
1 H NMR spectrum (CDCl3), δ, ppm: 1.2–2.2 m [8H,
(CH2)4, ring protons], 2.5 t (1H, ≡CH), 3.60 m (1H,
CHO), 4.20 m (1H, ICH), 4.25 d (2H, OCH2C≡C).
Found, %: C 40.49; H 4.58; I 48.52. C9H13IO. Calculat-
ed, %: C 40.91; H 4.96; I 48.07.
Cadmium chloride is applied as catalyst in a wide
range of organic reactions [5]. However no published
information exists on its use in reactions of iodoalkoxy-
lation, iodohydroxylation, and iodoacetoxylation.
We established that the reaction of alkenes with
propargyl alcohol, water, or acetic acid and crystalline
iodine catalyzed by CdCl2·2.5H2O was a convenient
preparation procedure for propargyl β-iodoethers [6, 7],
iodohydrine[2, 8], and iodoacetate [1, 2, 9] obtained in
75–85% yield.
6-Iodo-5-phenyl-4-oxa-1-hexyne (II) was similarly
obtained from propargyl alcohol, styrene, and iodine.
Yield 60.7 g (85%), bp 93–94°C (1 mm Hg), d420 1.5812,
nD20 1.5902 {yield 73%, bp 93°C (1 mm Hg), d420 1.5816,
nD20 1.5900 [7]}. H NMR spectrum (CDCl3), δ, ppm:
1
2.5 t (1H, ≡CH), 3.8 d (2H, OCH2), 3.38 d (2H, ICH2),
4.21 d (2H, OCH2C≡C), 4.25 m (1H, CHI), 7.30 m (5H,
C6H5). Found, %: C 46.12; H 3.60; I 44.12. C11H11IO.
Calculated, %: C 46.17; H 3.87; I 44.30.
1-Propargyloxy-2-iodocyclohexane (I). Into a stirred
R3CH=CHR1 + I2 + R2OH
.
CdCl2 2.5 H2O
5-Iodomethyl-4-oxa-1-nonyne (III) was similarly
obtained from propargyl alcohol, 1-hexene, and iodine.
Yield 51.8 g (78%), bp 83°C (1 mm Hg), d420 1.4588, nD20
1.5143 {yield 53%, bp 83°C (1 mm Hg), d420 1.4585, nD20
1.5140 [7]}. 1 H NMR spectrum (CDCl3), δ, ppm: 2.5 t
(1H, ≡CH), 3.60 m (1H, CHO), 3.38 m (2H, ICH2), 4.01
d (2H, OCH2C≡C), 0.85–1.25 m [9H, CH3, (CH2)3].
Found, %: C 38.45; H 5.4; I 50.52. C9H15IO. Calculated,
%: C 38.12; H 5.2; I 50.34.
R2OCH(R3)CH(R1)I
_
I V
R1, R3 = (CH2)4 (I, IV, V); R1 = H, R3 = Ph (II), Bu
(III), R2 = CH2C≡CH (I–III), H (IV), Ac (V).
mixture of 14 g (0.25 mol) of propargyl alcohol and
20.5 g (0.25 mol) of cyclohexene cooled to 5–10°C was
added 22 g (0.12 mol)of CdCl2·2.5 H2O, then was added
by portions of 1 g 63 g (0.25 mol) of finely dispersed
crystal-line iodine. The reaction mixture was stirred at
room temperature for 3 h, filtered, the filtrate was diluted
with 5% solution of NaHCO3, treated with 10% Na2S2O3
2-Iodocyclohexanol (IV) was similarly obtained
from water, cyclohexene, and iodine within 6 h. Yield
42.3 g (75%), mp 42–43°C (H2O) (mp 42°C [2, 8]).
1082

IODOALKOXYLATION, IODOHYDROXYLATION, AND IODOACETOXYLATION OF ALKENES
1083
3. Mahajan, V.A., Shinde, P.D., Gajare,A.S., Karthikeyan, M.,
and Wakharkar, R.D., Green. Chem, 2002, vol. 4, p. 325.
4. Yusubov, M.S., Yusubova, R.Ya., Filimonov, V.D., and Chi,
Ki-Van., Zh. Org. Khim., 2002, vol. 38, p. 944.
1-Acetoxy-2-iodocyclohexane (V) was similarly
obtained from cyclohexene, acetic acid, and iodine. Yield
67 g (85%), d420 1.6115 (d420 1.61 [2]). 1H NMR spectrum
(CDCl3), δ, ppm: 1.2–2.3 m [8H,(CH2)4, ring protons],
2.3 s (3H), 4.25 m (1H, CHI), 3.60 m (1H, CHO).
13C NMR spectrum (CDCl3), δ, ppm: 170.3, 71.3, 67.4,
38.3, 32.0, 27.4, 23.9, 21.6. Found, %: C 35.4; H 4.75;
I 47.00. C8H13IO2. Calculated, %: C 35.8; H 4.88; I 47.15.
5. Metody elementoorganicheskoi khimii. Khlor alifaticheskie
soedineniya (Methods of Organoelemental Chemistry.
Chlorine Aliphatic Compounds), Nesmeyanov, A.N. and
Kocheshkov, K.A., Ed., Moscow: Nauka, 1973, p. 752.
6. Talybov, G.M., Mekhtieva, V.Z., and Karaev, S.F., Zh. Org.
Khim., 2001, vol. 37, p. 634.
NMR spectra were registered on a spectrometer
Bruker DRX 300 M [300 (1H), 75 (13C) MHz].
7. Mekhtieva, V.Z., Talybov, G.M., Karaev, S.F., and
Teimurova, R.A., Izv. VTUZov Azerb., 2003, vol. 3, p. 28.
8. Sanseverino, A.M., de, Mattos, M.C.S. Synthesis, 1998,
vol. 11, p. 1584.
REFERENCES
1. Georgoulis, C. and Valery, J.M., Synthesis, 1978, vol. 5,
p. 402.
2. Iranpoor, N. and Shekarriz, M., Tetrahedron, 2000, vol. 56,
9. Shigeyasu, M., Masakichi, S., Yasuo, F., and Tatsuno, T.,
Chem. and Fharm. Bull., 1983, vol. 31, p. 1788.
p. 5209.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 5 2008