A Photoirradiative Phase-Vanishing
Method: Efficient Generation of HBr from Alkanes and Molecular Bromine
and Its Use for Subsequent Radical Addition to Terminal
Alkenes

Hiroshi Matsubara; Masaaki Tsukida; Daisuke Ishihara; Kenji Kuniyoshi; Ilhyong Ryu

doi:10.1055/s-0030-1258482

CLUSTER

A Photoirradiative Phase-Vanishing Method: Efficient Generation of HBr from Alkanes and Molecular Bromine and Its Use for Subsequent Radical Addition to Terminal Alkenes

Hiroshi Matsubara*, Masaaki Tsukida, Daisuke Ishihara, Kenji Kuniyoshi, Ilhyong Ryu*
Department of Chemistry, Graduate School of Science, Osaka Prefecture University, Sakai, Osaka 599-8531, Japan
Fax: +81(72)2549695; e-Mail: matsu@c.s.osakafu-u.ac.jp; e-Mail: ryu@c.s.osakafu-u.ac.jp;

Abstract

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Abstract

A triphasic phase-vanishing (PV) system comprised of an alkane, perfluorohexanes, and bromine was successfully combined by photoirradiation to efficiently generate hydrogen bromide, which underwent radical addition with 1-alkenes in the hydrocarbon layer to afford terminal bromides in high yields.

Key words

fluorous solvent - phase-vanishing - photoirradiation - bromination - hydrogen bromide

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References

References and Notes

<A NAME="RY01610ST-1">1</A> For a general review on fluorous chemistry, see: Handbook of Fluorous Chemistry Gladysz JA. Curran DP. Horváth IT. Wiley-VCH; Weinheim: 2004.

For reviews on fluorous solvents, see:

<A NAME="RY01610ST-2A">2a</A> Ryu I. Matsubara H. Emnet C. Gladysz JA. Takeuchi S. Nakamura Y. Curran DP. In Green Reaction Media in Organic Synthesis Mikami K. Blackwell Publishing; Oxford: 2005. p.59

<A NAME="RY01610ST-2B">2b</A> Matsubara H. Ryu I. In Green Separation Processes: Fundamentals and Applications Afonso CAM. Crespo JG. Wiley-VCH; Weinheim: 2005. p.219

<A NAME="RY01610ST-3">3</A> Matsubara H. Yasuda S. Sugiyama H. Ryu I. Fujii Y. Kita K. Tetrahedron 2002, 58: 4071

<A NAME="RY01610ST-4">4</A> Matsubara H. Maeda L. Ryu I. Chem. Lett. 2005, 34: 1548

<A NAME="RY01610ST-5">5</A> Matsubara H. Maeda L. Sugiyama H. Ryu I. Synthesis 2007, 2901

For reviews on the ‘Phase-Vanishing’ method, see:

<A NAME="RY01610ST-6A">6a</A> Ryu I. Matsubara H. Nakamura H. Curran DP. Chem. Rec. 2008, 8: 351

<A NAME="RY01610ST-6B">6b</A> Iskra J. Lett. Org. Chem. 2006, 3: 170

<A NAME="RY01610ST-7">7</A> Ryu I. Matsubara H. Yasuda S. Nakamura H. Curran DP. J. Am. Chem. Soc. 2002, 124: 12946

<A NAME="RY01610ST-8A">8a</A> Nakamura H. Usui T. Kuroda H. Ryu I. Matsubara H. Yasuda S. Curran DP. Org. Lett. 2003, 5: 1167

<A NAME="RY01610ST-8B">8b</A> Matsubara H. Yasuda S. Ryu I. Synlett 2003, 247

<A NAME="RY01610ST-8C">8c</A> Rahman MT. Kamata N. Matsubara H. Ryu I. Synlett 2005, 2664

<A NAME="RY01610ST-8D">8d</A> Matsubara H. Tsukida M. Yasuda S. Ryu I. J. Fluorine Chem. 2008, 129: 951

<A NAME="RY01610ST-9A">9a</A> Jana NK. Verkade JG. Org. Lett. 2003, 5: 3787

<A NAME="RY01610ST-9B">9b</A> Iskra J. Stavber S. Zupan M. Chem. Commun. 2003, 2496

<A NAME="RY01610ST-9C">9c</A> Curran DP. Werner S. Org. Lett. 2004, 6: 1021

<A NAME="RY01610ST-9D">9d</A> Podgoršek A. Stavber S. Zupan M. Iskra J. Eur. J. Org. Chem. 2006, 483

<A NAME="RY01610ST-9E">9e</A> Windmon N. Dragojlovic V. Tetrahedron Lett. 2008, 49: 6543

<A NAME="RY01610ST-9F">9f</A> Windmon N. Dragojlovic V. Beilstein J. Org. Chem. 2008, 4: 29

<A NAME="RY01610ST-9G">9g</A> Ma K. Li S. Weiss RG. Org. Lett. 2008, 10: 4155

<A NAME="RY01610ST-9H">9h</A> van Zee NJ. Dragojlovic V. Org. Lett. 2009, 11: 3190

<A NAME="RY01610ST-9I">9i</A> Pels K. Dragojlovic V. Beilstein J. Org. Chem. 2009, 5: 75

^¹H NMR of the concentrated reaction mixture in entry 6 of Table 1 shows peaks assigned to 2-bromo-2,4,4-trimethyl-pentane as the product, suggesting that hydrogen abstraction from isooctane would occur selectively at the tertiary position of isooctane.

<A NAME="RY01610ST-11A">11a</A> Brown HC. Lane CF. J. Am. Chem. Soc. 1970, 92: 7212

<A NAME="RY01610ST-11B">11b</A> Brown HC. Lane CF. Tetrahedron 1988, 44: 2763

<A NAME="RY01610ST-11C">11c</A> Falorni M. Lardicci L. Giacomelli G. J. Org. Chem. 1986, 51: 5291

<A NAME="RY01610ST-11D">11d</A> Brown HC. Lane CF. J. Am. Chem. Soc. 1970, 92: 6660

<A NAME="RY01610ST-11E">11e</A> Brown HC. Lane CF.
J. Chem. Soc. D: Chem. Commun. 1971, 521

<A NAME="RY01610ST-11F">11f</A> Lane CF. Brown HC. J. Organomet. Chem. 1971, 26: C51

<A NAME="RY01610ST-11G">11g</A> Tufariello JJ. Hovey MM. J. Chem. Soc. D: Chem. Commun. 1970, 372

<A NAME="RY01610ST-11H">11h</A> Kabalka GW. Sastry KAR. Hsu HC. Hylarides MD. J. Org. Chem. 1981, 46: 3113

<A NAME="RY01610ST-11I">11i</A> Maruoka K. Sano H. Shinoda K. Nakai S. Yamamoto H. J. Am. Chem. Soc. 1986, 108: 6036

<A NAME="RY01610ST-11J">11j</A> Tufariello JJ. Hovey MM. J. Am. Chem. Soc. 1970, 92: 3221

<A NAME="RY01610ST-12A">12a</A> Tamao K. Yoshida J. Takahashi M. Yamamoto H. Kakui T. Matsumoto H. Kurita A. Kumada M. J. Am. Chem. Soc. 1978, 100: 290

<A NAME="RY01610ST-12B">12b</A> Tamao K. Yoshida J. Yamamoto H. Kakui T. Matsumoto H. Takahashi M. Kurita A. Murata M. Kumada M. Organometallics 1982, 1: 355

<A NAME="RY01610ST-13A">13a</A> Hart DW. Schwartz J. J. Am. Chem. Soc. 1974, 96: 8115

<A NAME="RY01610ST-13B">13b</A> Tolstikov GA. Miftakhov MS. Valeev FA. Izv. Akad. Nauk SSSR, Ser. Khim. 1979, 2576

<A NAME="RY01610ST-14A">14a</A> Isagaga K. Tatsumi K. Otsuji Y. Chem. Lett. 1977, 1117

<A NAME="RY01610ST-14B">14b</A> Sato F. Sato S. Kodama H. Sato M. J. Organomet. Chem. 1977, 142: 71

<A NAME="RY01610ST-14C">14c</A> Lee H.-S. Kim C.-E. J. Korean Chem. Soc. 2003, 47: 297

<A NAME="RY01610ST-14D">14d</A> Lee H.-S. Lee G.-Y. J. Korean Chem. Soc. 2005, 49: 321

<A NAME="RY01610ST-14E">14e</A> Gavrilenko VV. Kolesov VS. Zakharkin LI. Izv. Akad. Nauk SSSR, Ser. Khim. 1985, 681

The reaction without fluorous phase gave an inferior result. For example, irradiation of a mixture of bromine (1.16 mmol) and isooctane (6 mL) with a 500 W Xe lamp for 30 min, followed by addition of 1-dodecene (1 mmol) at r.t., gave 1-bromododecane in 79% yield together with unreacted 1-dodecene (11%). In this procedure, probably some HBr generated would outgas during the reaction.

<A NAME="RY01610ST-16">16</A> For an example of the use of HBr to prepare key substrates for sequential radical reactions, see: Zhang W. Hua Y. Geib SJ. Hoge G. Dowd P. Tetrahedron 1994, 50: 12579

Typical Procedure for Photoirradiative Phase - Vanishing Hydrogen Bromide Addition to Alkenes (Table 2, entry 2): FC-72 (6 mL) was placed in a Pyrex test tube (13 mm
Æ × 105 mm) to which bromine (2.1 mmol, 340 mg) was added slowly using a glass pipette. Isooctane (1.5 mL) solution of 1-dodecene (2.0 mmol, 340 mg) was then added slowly, forming three layers. The test tube was irradiated with a 500 W Xenon lamp for 2 h. The isooctane layer was taken up with a pipette. Then, additional hexane (4 × 4 mL) was placed on the residual FC-72 layer, followed by decanting off. The combined organic layer was washed with aq 10% Na₂S₂O₃ (30 mL) and sat. brine (30 mL), dried over Na₂SO₄, and concentrated. Purification by a short column chromatography on silica gel with hexane gave 1-bromo-dodecane (480 mg, 96%).

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