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35.2.5.1.4 Method 4: Hydroxy- and Alkoxybromination of Alkenes

DOI: 10.1055/sos-SD-035-00431

Troll, T.Science of Synthesis, (200735471.

The first step in the electrophilic addition of bromine to alkenes is the formation of a cyclic bromoniun ion or an open-chained carbenium ion. When this intermediate is trapped by water or alcohols, α-hydroxy- or α-alkoxyalkyl bromides are formed. This reaction is a side reaction during the addition of bromine in water or alcohol as a solvent, but can be done in a preparative way by the addition of hypobromous acid to alkenes. Hypobromous acid can be generated by the addition of acid to a solution of bromine in aqueous alkali. The hydroxybromination is then best carried out in neutral or weakly acidic solution in order to avoid further reactions of the bromohydrins (hydroxy bromides). Some examples of the hydroxybromination of alkenes with hypobromous acid are given in Table 10.

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Meeeeeee Meeeeeee Meeeeee Mee
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Mee eeeeeeeeeeeeee ee ee eeeeeee ee eeeeeeeee eeee Meeeeeeeeee'e eeee, eee ee eeeeeeeee ee eeeeeeee eeee eeeeeeeeeeeeeeeeeeeee (Meeeee 88).[‌888‌]

Meeeee 88 Meeeeeeeeeeeeeeeee ee Meeeeeeeeeeeeeeeeeeee[‌888‌]

α,β-Meeeeeeeeee eeeee eeee eee α-eeeee-β-eeeeeee eeee.[‌888‌,‌888‌] Meee-8,8-eeeee,[‌888‌] 8-eeeeeeeeee-8,8-eeeee,[‌888‌] 8-eeeeeeeee-8,8-eeeee,[‌888‌] eee 8-eeeeeeeeee-8,8-eeeee[‌888‌] eeee 8-eeeee-8-eeeeeee eeeeeee ee eee eeee-eeeeeeeeeee eeeeee eeee; eeee eeeeeeee, 8,8-eeeeeeee eeeeeeee (Meeeee 88).[‌888‌]

Meeeee 88 Meeeeeeeeeeeeeeeee ee 8-Meeeeeeeee-8,8-eeeee eee Meeeeeee[‌888‌,‌888‌]

Meeeeeeeeee eeee eee eeee ee eeeeeeeee eeee eeeeee eeeeeee ee eeeeeeeee eeee eeeeee eeeeeeee eeeeeee. Me eee eeeeeeee ee eeeeeee, eeeeeeeeeeeeeeeeee eee ee eeeeeeee ee eeee eeeeee, e.e. ee eeee 88 (Meeeee 88).[‌888‌] Mee eeeeeeeeeeeeeeee ee eee eeeeeeee ee ee eeeeeeeee eeee Meeeeeeeeee'e eeee eee ee eee eeee eeeeeeee eeeeeee eee 8,8-eeeeeeeeeeeee eeeeeee. Mee eeeeeeeeeeeeeeeee ee eee eeeeeeee ee eeeee eee eee eeeeeeee eeeee.

Meeeee 88 Meeeeeeeeeeeeeeeee eeee Meeeee MeeeeeeMeeeee Meeeeeee Meeeeee[‌888‌]

Meeeeeeeeee 88

Meeeee Meeeeee Meeee (%) Mee
88+88 [‌888‌]
88+88 [‌888‌]
88 [‌888‌]
88 [‌888‌]
88 [‌888‌]
88+88 [‌888‌]
88 [‌888‌]
88 [‌888‌]
88 [‌888‌]
88 [‌888‌]
88 [‌888‌]
88 [‌888‌]

Meeeeee eeee eeeee ee eeee eeeeeeeeeeee eeee M-eeeeeeeeeeeeeeee ee eeeee eeeeeeee eeeeeeeee.[‌888‌] Meeeeeeeeee eeeeeeeeeee ee eeeeeeee ee eee eeeeeee ee eeeeee eeeeeeeeeeee. Meee M- eee M-eeeeeeee eeeeeee (eeeeeeee, 8,8-eeeeeeeeeeee-8-eee) eeee eeeeeeeeeee (M,M/M,M)- eee (M,M/M,M)-eeeeeeeeeeee ee eeeee eeeeeeee. Meeeeeee-eeee eeeeeee (eeeee, eeeeeeeeeee eeeee) eeee ee eeeee eeeee eeeee eeeeeeeeee. Meeeeeeeeee eeeee eee eeeee-eeeeeeeeeee ee 88% eeeee[‌888‌] eee eeeeee eeeee eeeee-8-eeeee-8-eeeeeeeeeeeee.[‌888‌] Mee eeeeeeee ee eeeee eeee eeee M-eeeeeeeeeeeeeeee ee eeeeee eeee eeeee eee α-eeeeeeeeeeee.[‌888‌]

Mee eeeeeeee ee eeeeeeeeee eeee M-eeeeeeeeeeeeeeee ee eeeee eeeeeeee eeeeeeeee eeeee ee e eeeeeee ee eeeeeeeeee eeeeeeee.[‌888‌] Mee eeeeeeee ee eeeeeeeeeee eeeeeeeeeeeee 88 eeee M-eeeeeeeeeeeeeeee eee eeeee ee eeeeeee eeeee ee e eee-eeeeee 88 eee e eeeeeeeeee eeeeee 88 (Meeeee 88).[‌888‌]

Meeeee 88 Meeeeeeeeeeeeeeeee ee Meeeeeeeeeee[‌888‌]

Meeee eeeeeeee eeee eee eeeeeeeeeeeeeeeeee eee M-eeeeeeeeeeeeee eee M,M-eeeeeeeeeeeeeeeeeeeeeeeee.[‌888‌‌888‌] Meee eeee ee eeeeeeeeeeeeeee eeeeeeee, eeeee eeeeeeee eeee eeee eeeeeeee ee eeeeeeeeeeeee.[‌888‌,‌888‌,‌888‌]

Meeeeee eeeeeee eeeeeeeeeeeeeeeeee eeeee eeeeee eeeeeeeeee eeee M-eeeeeeeeeeeeeeee ee eeeee eeeeeee (Meeeee 88).[‌888‌] 8-Meeee-8-eeeeeeeeeeeeeeeee eeeeeeeeeeeeeeeee ([eeee]MM8)[‌888‌] ee ee eeeee eeeeee eeee ee eeeeee ee eee eee eeeee eee eeeee eee ee eeeeeeee. Meeeeeeeeeee eee ee eeeeeeee ee eeee eeeeee. Mee eeeeeeeeeeeeeeee ee eee eeeeeeee ee eeee, eeee eee eeeeeeeee ee eeeeeeee eeeeeee, eee eee eeeeeeeeeeeeeeeee ee eeeee.

Meeeee 88 Meeeeeeeeeeeeeeeee ee Meeee Meeeeee[‌888‌]

Meeeeeeeeee 88

Meeeee Meeeeee Meee (e) Meeee (%) Mee
8 88 [‌888‌]
8.8 88 [‌888‌]
8.8 88e [‌888‌]
8.8 88 [‌888‌]
8.8 88 [‌888‌]
8.8 88 [‌888‌]
8.8 88 [‌888‌]
8.8 88 [‌888‌]
8.8 88 [‌888‌]
8.8 88 [‌888‌]
8.8 88 [‌888‌]
8.8 88e [‌888‌]

e Me8=8-MeM8M8.

e Me e 88:88 eeeee.

Mee eeee ee eeeeeeee eee ee eeee eeee eeee eeeeeeee-eeee eeeeeee, eeeee eeeeeeeee eeeeeee eeeeeeee eeeeeeeeeeeee eeeeeeee. Meeee eee M-eeeeeeeeeee, M-eeeeeeeeeeeeee ee e eeee eeeeeeeee eeeeeee eee eee eeeeeeeee ee eeeeeeeeeeee 88 eeee eeeeeee[‌888‌] eee eeee eeee α,β-eeeeeeeeeee eeeeeeee eeeeeeeee (Meeeee 88).[‌888‌]

Meeeee 88 Meeeeeeeeeeeeeeeee eeee M-Meeeeeeeeeeeee[‌888‌]

Meeeeeeeeee 88

M8 M8 M8 Meee (eee) Meeee (%) Mee
(MM8)8 M 88 88e [‌888‌]
Me M M 88 88e [‌888‌]
Me M M 88 88 [‌888‌]
Me M Me 88 88 [‌888‌]

e eeeee Meeeee.

e Meeeeee ee eeeeeeeeeeee (8:8).

M-Meeeeeeeeeeeee eee eeee ee eeee eee eee eeeeeeeeeee ee eeeeeeeeeeee 88 ee α,β-eeeeeeeeeee eeeeeeee eeeeeeeee (Meeeee 88).[‌888‌] M-Meeeeeeeeeeeee eeee eeeeee eeee 8-eeeeeeeeeeeeeeeeeee ee eeee eee eeeeeeeeeeeee eeeeeeeeeee ee 88% eeeee.[‌888‌]

Meeeee 88 Meeeeeeeeeee ee Meeeeeeeeee Meeeeeee Meeeeeeee[‌888‌]

Meeeeeeeeee 88

Meeeee Meeeeee Meee (eee) Meeeee (%) Mee
88 88 [‌888‌]
88 88 (88) [‌888‌]
88 88 (88) [‌888‌]
88 88 (88) [‌888‌]
88 88 (88) [‌888‌]
8 88 (88) [‌888‌]

e Meeee eeeee eeeeeeeeeeee ee eeeeeeeeeee.

Meeeeee eeeeee eeeeeeeee eeee eee eeeeee eeee ee eee ee eeeee eeeeee eeeee eee eeeeeeeeeee ee eeeeeeeeeee eeeeeeeee. Mee eeeeeeeee eee ee eeeeeeee ee eee eeeeeee eeeee ee eee eeeeeeee eeeeee eeee, eeeeeee e eeee-eeeeeeee eeee (Meeeee 88).[‌888‌,‌888‌]

Meeeee 88 Meeeeeeeeeeeeeeeee eeee Meee Meeeeee[‌888‌]

Meeeeeeeeeeee ee eeeeee eeeee eeeeee eee eeeeeeeeeeeeeeeeee ee ω-eeeeeeeeeeeeeeeee eee eeee eeeeeeeee.[‌888‌] M eeeeeeeeeeee eeeeeeee eee ee eeeeeeee eeee eeeeeeee-8,8-eeeee (Meeeee 88).[‌888‌]

Meeeee 88 Meeeeeeeeeee Meeeeeeeeeeeeeeeee[‌888‌]

Mee eeeeeeeeee ee eeeeeeeeeeeee eeeeeee eeee Meeeeeeeeee (eee Meeeeee 88.8.8.8.8.8) ee eeeeeeee ee eeeee ee e eeeeeeeee eeeee ee eeeeeeeeeeeeeeeee ee eeeeeeeeeeeeeeeeee. Meeee eeeee eeeeeeeeee, eeeeeeeeeeeeee eeeeee ee e eeeeeee eeeee eee eeee eeee eeeee (Meeeee 88).[‌888‌]

Meeeee 88 Meeeeeeeeeeeeeeee eeee Meeeeeeeeee eee Meeeeeeeeeeeee Meeeeeeeeeeeeeeee[‌888‌]

Mee eeeeeeeee ee eeee-eeeeeeee eeeee ee eeeeeeeee eeeeeee, eee eee-eeeeeeee eeeee eee eeee ee eeeeee (Meeeee 88).[‌888‌] Meee M8 ee eee eeeeeeeeeeeeeeeeeee 88 ee e eeeeee eeeee, eeee eee eeeee eeeeeeeeee 888 eee ee eeeeeeee.

Meeeee 88 Meeeeeeeeeeeee Meeeeeeeeeee ee Meeeeeeeeeeeeeeeeee[‌888‌]

Mee eeee eeeeeeeeeee ee eeeeeeeeeeeeeeeeee ee eee eeeeeeeeeeeeeeeeee eeeeeeeee ee eeeeeeeeeeeee eeeeee eeeeeeeeeee eeeeeeeeeeeeeee eeeee. Mee eeeeeeeee ee eeeeeeeee eeeeeeee ee eee eeeeeeee eee eeee eeeeeeeeeeee eeeee e eeeeeeeeee-eeeee eeeeeeeee eeeee eeeee ee MM8 eeeeeeeeeeee.[‌888‌] Meeeeeeeeeeeeeeeeee eee eeee eeee eee eee eeeeeeeeeeeeeeee eeeeeeeee ee eeeeeeeeeeeeeee eeeeee,[‌888‌,‌888‌] eeeeeeeeeee, eee eeeeeeeeeeeeee,[‌888‌] eeeee eee eeeee eeeeeeee ee eee eeeeeee eee eeeeeee.

M eeeeeeee eeeee eee eeee eee ee ee eeeeeeeeeeeeee eeeeeeeeeee. Mee eeeeeeeee ee eeeeeeeeeeee eeee β-eeeeee-γ,δ-eeeeeeeeeee eeeeeeeeee eeeeeeee eee eeeeeeeeeeeee ee eee eeeeeeee eeeee, eeee eeeeeeeee ee eee eeeeeeeee eeeeeeeeeeeee (Meeeee 88);[‌888‌] eeeeeee eeeeeeee eee eeeee ee Meeee 88.[‌888‌]

Meeeee 88 M Meeeeeeeeee eeee e Meeeee Meeeeeeee[‌888‌]

Meeee 88 Meeeeeeeeeee eeee Meeeee Meeeeeeeee[‌888‌]

Meeeeeeee Meeeeee Meeee [eeee/eee (M8/M8)] Meeee (%) Mee
>88:<8 88 [‌888‌]
>88:<8 88 [‌888‌]
8:8 88 [‌888‌]
>88:<8 88 [‌888‌]
>88:<8 88 [‌888‌]
>88:<8 88 [‌888‌]
<8:>88 88 [‌888‌]

Meeeee eeeeeeeee eeeeeeee eeeeee ee eeeeeee eeeeeee. Me eee eeeeeeee ee eeeeeee, eeeeeeeeee eee eeeeeeee. Me eeeeeee eeeeeeee eeee eeeeeeeeeeee/eeeee ee eeeeeeeeeeee/eeeeeeee, eeeeeee eeeeeeee ee eeeeeee eeeeeeee eee ee eeeeeeee ee eeeeee ee ee 88% (Meeeee 88).[‌888‌] Mee eeeeeeeeee eeeeeee ee eeee eeeeeeeeeeeeeeeeee ee eeeeeeeeeee eeeeeeee eeeee eeeeeeeeeeee eeee β-eeeeeeeeeeee eeeee ee eeeeeeeeeeee eeeeee eeeeee ee 8888% eeeee eeeeeeeeee eeee eee eeeeeeee.[‌888‌]

Meeeee 88 Meeeeeeeeeeeeeeee eeee Meeeee Meeeeeeee[‌888‌]

α,β-Meeeeeeeeee eeeeeeee eeeeeeeee eeee eeeeee eeeeeeee, eeee eee eeeeeee eeee eeeeeeee ee eee eeeeeeee eeeee (Meeeee 88).[‌888‌]

Meeeee 88 Meeeeeeeeeeeeeeeee ee 8-Meeeeeeee-8-ee-8-eee[‌888‌]

Meeeeee eeeee eeeeeeeee eeee ee eeeeeeeeeeeeeeeeeeee (888), M-eeeeeeeeeeeeee (888), eee 8,8,8,8-eeeeeeeeeeeeeeeeeee-8,8-eeee-8-eee (888) eee eeee ee eeee ee eeeeeeeeeee eeeeee ee eeeeeeee, eeeeeee eeeeeee eeeeeeee (Meeeee 88 eee Meeee 88).

Meeeee 88 Meeeeee Meeee Meeeeeeee Meee eee Meeeeeeeeeeeeeeeee

Meeee 88 Meeeeeeeeeeeeeeeee eeee Meeeeee Meeee Meeeeeeee[‌888‌‌888‌]

Meeeee Meeeeee Meeeeee Meeeeee Meeee (%) Mee
888
888
888
88
88
88
[‌888‌]
[‌888‌]
[‌888‌]
888 88 [‌888‌]
888 88 [‌888‌]
888 88 [‌888‌]
888 88 [‌888‌]
888 88 [‌888‌]
888 88 [‌888‌]
888 88 [‌888‌]
888 88 [‌888‌]

e Mee Meeeee 88 eee eeeeeeeeee.

Meeeeeeee eeeeeeeee ee e eeeeeeeeeeeeee-eeeeeee eeeeee eeeeeeeee ee e eeeeeeeeeeeee eeeeeeee ee eee eeeeeeeee ee eeeeeee eeee eeeeeeee eeeeeeee, eeeeeeeee eeeeeeeeeeeeeeeeee eee eeeeeeeeeeeeeeeee eeeeeeee ee eee eeeeeeee ee eeeeeee (Meeeee 88).[‌888‌] Meeeeeeeeeeeeeeeee eee ee eeeeeee eee eeeee eeeeeee eeeeeeeeee, eeeee eeeee eeeeeee ee eeeeeeee ee eee eeeeeee. Meee ee eee eeeeeee ee Meeeee 88 eeee eee eeeeeeeeeeeee α-eeeee eeeeeee eeee eeeeeee eeeee- eee eeeeeeeeeeeeeeeeeee.

Meeeee 88 Meeeeeeeeeeeeeeee eeee Meeeeeeeeeeee Meeeeeeee[‌888‌]

Meeeeeeeeee 88

Meeeee M8M8 (eeeee) Meeeeee Meeee (%) Mee
8.8 88e [‌888‌]
8.8 88 [‌888‌]
8.8 88 [‌888‌]
8.8 88 [‌888‌]
8.8 88 [‌888‌]
8.8 88 [‌888‌]
8.8 88e [‌888‌]
8.8 88e [‌888‌]
8.8 88 (88:88) [‌888‌]
8.8 88 (88:88) [‌888‌]
8.8 88 (88:88) [‌888‌]
8.8 88 (88:88) [‌888‌]
8.8 88 (88:88) [‌888‌]
8.8 88 (88:88) [‌888‌]
8.8 88 (88:8) [‌888‌]

e Me8=8-MeMM8M8.

e Meeeeeee eeeee.

Meee β,γ- eee γ,δ-eeeeeeeeeee eeeeeeeeee eeeee eeeee eeeee eeeeeeee eeee eeeeeeee eeee eeeeeeeeeeeee eeeeeee (Meeeee 88).[‌888‌,‌888‌]

Meeeee 88 Meeeeeeeeee ee Meeeeeeeeee Meeee[‌888‌,‌888‌]

Meeeeee eeeeee ee eeeeeeeeeeeee eeeeeee ee (eeeeeeeeeeeee)eeeeeee eee eeeeeee eeeeeee.[‌888‌] Mee eeeee eeeeeee ee eeee-8-eeeee eeee eee ee eeeeeeee ee 88% eeeee eeee eeee eeeeeee ee eeeeeeeeeeeeeee ee eeee eeeeeeeeeee. Meeeeeeeeee-8-eeeeeeeeee eeee eeeee eee eeeee eeeeeee 888.[‌888‌] Meeeeeeeee-eeee-8-eeeeeeeeee eeee eeee eeeee e eeeee eeeeeee 888 eeee eeeeeeee eeee eeeeeee.[‌888‌] α-Meeeeeeeeeeee eee eeeeeeee eeee eee eeeeeeeeeeee eeeeeeeee eee ee eeeeeee ee eeeeeee (Meeeee 88).[‌888‌]

Meeeee 88 Meeeeeeee ee Meeee Meeeeeee eee e Meeeeeeeeeee[‌888‌‌888‌]

Meeeee eeeeee 888 ee α,β-eeeeeeeeeee eeeee eee ee eeeeeeee eeee eee eeeeee eee eeeeeee. Mee eeeeee eeeeeeeeeee ee eeeeeee ee eeeeeeeeeee ee eee α- eee β-eeeeeeeee ee eee eeeeeeeeeeeeee eeeeee eeee eeeeee eee eeeeeeeee ee eee eeeeeeeeeeeee 888 eee 888 eeee M-eeeeeeeeeeeeeeee (Meeeee 88).[‌888‌,‌888‌] Meee eeeeeeeee eee eeee eeee ee eee eeeeeeeee ee eeeeeeeee eeeeee eeeeeeeee eeee ee eeeeeeeeeeeeeeee,[‌888‌] 8,8-eeeeeee-8M-8-eeeeeeeeee-8-eeeeeeeeee eeee,[‌888‌] 8-eeeeeee-8-eeeeeeeeeeeeee eeeee,[‌888‌] eee α,β-eeeee eeeeeeeee.[‌888‌]

Meeeee 88 Meeeeeeeee Meeeeeeeeeeeeeeeee[‌888‌,‌888‌]

Meeeeeeeeeee Meeeeeeee

8-Meeeeeeeee-8-eee 88; Meeeeee Meeeeeeee:[‌888‌]

MeMeM8 (88eeee) eee eeeeeeeee ee M8M (8eM) eee eee eeee eee eeeeeeee ee eM8 eeee 8M M8MM8. Mee eeeeee (88eeee) ee MeMM (88eM) eee eeeee. Meee e 8M eeee ee MeMMM8 (88eM) eee eeeee eeeeeeee eeee e eeeeee ee eeeee 8e eee eee eeeeeee eee eeeeeee ee 88°M eee ee eeeeeeeeee 8e. Mee eeeeeeeee eeee eee eeeeeeeee eeee Me8M (8×888eM), eee eee eeeeeeee eeeeeee eeeeee eeee eeeeee eeee ee Me8MM8 eeee, eee eeeee (MeMM8). Meeeeee ee eee eeeeeee eeeee eeeeeee eeeeeeee eeee eee eeeee eeeeeee, eeeee eee eeeeeeee ee eeeeee eeeeeeeeeeeeee (eeeeee eee); eeeee: 8888%.

8-Meeeeeeeee-8-eee 88; Meeeeee Meeeeeeee:[‌888‌]

M-Meeeeeeeeeeeee (8eeee) eee eeeee ee e eeeeeee eeee ee eee eeeeee (8eeee) ee M8M/eeeeeee (8:8, 88eM) ee ee. Meeee eeeeeeeeeee ee eee eeeeeeee, Me8M (88eM) eee eeeee. Mee eeeeeee eeeee eee eeeeee eeee 88% MeMMM8 (8×8eM) eee 88% MeMMM8 (8×8eM), eee eeeee (Me8MM8). Meeeeee ee eee eeeeeee eeeee eeeeeee eeeeeeee ee e eeeeee eeeeeeeeee eeee eee eeeeeee; eeeee: 8888%.

8-Meeee-8-eeeeeee Meeeeeee Meeeeeeee 88; Meeeeee Meeeeeeee:[‌888‌]

Mee eeeee (8.8eeee) eee M-eeeeeeeeeeeeee (8.8eeee) ee M8M (88eM) eeee eeeeeee ee ee eeeee eeeeeeee eeeeeeeeee ee eee eeeee. Me8M eee eeeee eee eee eeeeeee eeeee eee eeeeee eeee eeeee ee MeMMM8, MeMMM8, eee M8M, eee eeee eeeee (Me8MM8). Mee eeeeeee eee eeeeeee eeeee eeeeeee eeeeeeee, eee eee eeeeeee eee eeeeeeee ee eeeeeeeeeeeeeee ee eeeeee eeeeeeeeeeeeee; eeeee: 8888% (8888% eeeee eeeeeeeeeeee).

References