ChemInform Abstract: Iodoalkoxylation, Iodohydroxylation, and Iodoacetoxylation of Alkenes Catalyzed by CdCl2×2.5H2O

Autor: V. Z. Mekhtieva, S. F. Karaev
Rok vydání: 2009
Předmět:
Zdroj: ChemInform. 40
ISSN: 1522-2667
0931-7597
DOI: 10.1002/chin.200905029
Popis: 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. 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 iodoalkoxylation, 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. 1-Propargyloxy-2-iodocyclohexane (I). Into a stirred 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), d4 1.5218, nD 1.5503 {yield 62%, bp 115°C (1 mm Hg), d4 1.5215, nD 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. Calculated, %: C 40.91; H 4.96; I 48.07. 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), d4 1.5812, nD 1.5902 {yield 73%, bp 93°C (1 mm Hg), d4 1.5816, nD 1.5900 [7]}. 1H NMR spectrum (CDCl3), δ, ppm: 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. 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), d4 1.4588, nD 1.5143 {yield 53%, bp 83°C (1 mm Hg), d4 1.4585, nD 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. 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]). + I2 + R2OH CdCl2 2.5 H2O R2OCH(R3)CH(R1)I R3CH=CHR1
Databáze: OpenAIRE
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