In the Laboratory

Regioselective Hydrochlorination
An Experiment for the Undergraduate Laboratory
Philip Boudjouk,* Beon-Kyu Kim, and Byung-Hee Han
Center for Main Group Chemistry, Department of Chemistry, North Dakota State University, Fargo, ND 58105

As pointed out by Kropp et al., hydrohalogenation is not PCl3 produced hydrochlorinated products in acceptable
a simple matter unless the double bond is activated by yields but that chlorotrimethylsilane was the most gener-
structural or electronic features (1). Using surface-mediated ally useful reagent. In this procedure, these compounds
reactions, Kropp et al. developed greatly simplified hydro- evolve hydrogen chloride at rates much faster than
halogenation procedures by using SiO2 or Al2O3 with a vari- chlorotrimethylsilane.
ety of active halides such as SOCl2, (COCl)2, Me3SiBr, and Chemoselectivity and regioselectivity were investigated
PI 3 , which feature higher yields and improved using (R)-carvone. (5R)-5-(1-Chloro-1-methylethyl)-2-
stereoselectivity over earlier methods (2). They postulated methylcyclohex-2-enone1 was obtained in 84% yield. Trace
that the hydrogen halide is formed via hydrolysis of the amounts of carvacrol are formed after 20 min. After 3 h, only
active halides by surface-bound water on the alumina or carvacrol is detected in the product mixture.
silica gel. Some of these procedures have been modified for
instructional purposes (3). Although these methods are
1.71 (s) 2.31 (s)
simple, precaution should be exercised in using oxalyl
6.71 (m) CH3 6.71 (m) CH3 CH3
chloride. Here we report a simple, convenient, and efficient H O H OH
O
procedure for the hydrochlorination of a variety of olefins Me3SiCl 3h
H2O, rt , 20min
using chlorotrimethylsilane and water: H Cl H CH(CH3)2 1.31 (d)
H3C C CH H3C C
2 CH3 (84%)

H 1.75 (s) 4.75 (db) 1.57 (d) arom H'S at 7.5

Me3SiCl, H2O
rt
Cl
Our results are summarized in Table 1. As shown in Table 1,
regioselectivity is high. Markovnikov (electrophilic) addition
(4) dominates for simple olefins and anti-Markovnikov (nu-
cleophilic) addition (5) for α,β-unsaturated olefins.
Our procedure calls for simple glassware and requires
no solvent, and for most olefins, the reaction is complete
within 5 h at room temperature. Product isolation is
straightforward, requiring evaporation of unused
chlorotrimethylsilane and hexamethyldisiloxane and, when
necessary, distillation of the desired product. Heating the
reaction mixture does not always lead to faster rates and
often results in lower yields, presumably from increased
vaporization of hydrogen chloride. We also found that
active chlorides such as SiCl4 , Me2 SiCl2, SOCl2, SnCl4, and
The stereochemistry of the hydrochlorination can be
studied using octalin. Formation of the trans product is eas-
ily followed by IR spectroscopy as the diagnostic band at
543 cm {1 increases (6).
Experimental Procedure
In a typical experiment, a 50-mL two-necked flask was
charged with 5.00 mL (4.03 g, 75.9 mmol) of acrylonitrile and
mixed with water (0.68 mL, 37.9 mmol) at room temperature.
After stirring this two phase system for 5 min, chlorotri-
methylsilane (11.45 mL, 9.90 g, 91.1 mmol) was added by
syringe. After 2 h, the residual water was taken up by ad-
dition of anhydrous sodium sulfate. Fractional distillation
removed excess chlorotrimethylsilane (bp 56 °C) and hexa-
methyldisiloxane (bp 99 °C). The remaining liquid was iden-

Table 1. Hydrochlorination of Olefins Using Chlorotrimethylsilane and Water

Time Yielda
Olefin Product Mechanism
(h) (%)
CH3CH2C(CH3)=CHCH3 2 CH3CH2C(CH3)ClCH2CH3 98 Electrophilic addition
CH3CH2CH2C(CH3)=CH2 3 CH3CH2CH2C(CH3)2Cl 91 Electrophilic addition
CH3CH2CH=C(CH3)2 3 CH3CH2CH2C(CH3)2Cl 96 Electrophilic addition
CH2=CHOCOCH3 2 CH3CHClOCOCH3 93 Electrophilic addition
CH3CH=CHCOCH3 5 CH3CHClCH2COCH3 80 Nucleophilic addition
CH2=CHCN 3 ClCH2CH2CN 89 Nucleophilic addition
CH2=CHCOCH3 5 ClCH2CH2COCH3 98 Nucleophilic addition
CH2=CHCOOCH2CH3 2 ClCH2CH2COOCH2CH3 95 Nucleophilic addition
a
All yields are isolated yields.

*Corresponding author.

Vol. 74 No. 10 October 1997 • Journal of Chemical Education 1223

In the Laboratory
tified as 3-chloropropionitrile (bp 174 °C [7] 174–176 °C,
89%). 1H-NMR (270 MHz, CDCl3) 2.87 (t, 2H), 3.72 (t, 2H).
Acknowledgment
Financial support from the National Science Founda-
tion through grant OSR-9452892 is gratefully acknowl-
edged.
Note
1. 1H-NMR (CDCl 3, d): 1.57 (d, 6H), 1.81 (s, 3H), 2.1–2.8
(m, 5H), 6.7 (m, 1H).
Literature Cited
1. Kropp, P. J.; Daus, K. A.; Crawford, S. D.; Tubergen, M. W.;
Kepher, K. D.; Craig, S. L.; Wilson, V. P. J. Am. Chem. Soc.
1224 Journal of Chemical Education • Vol. 74 No. 10 October 1997
1990, 112, 7433.
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Craig, S. L.; Wilson, V. P.; Bailargeon, M. M.; Breton, G.
W. J. Am. Chem. Soc. 1993, 115, 3071; Kropp, P. J.;
Crawford, S. D. J. Org. Chem. 1994, 59, 3102.
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4. Marcuzzi, F.; Melloni, G.; Modena, G. Tetrahedron Lett. 1974,
5, 413; Fahey, R. C.; McPherson, C. A. J. Am. Chem. Soc.
1971, 93, 2445.
5. March, J. Advanced Organic Chemistry, 4th ed.; Wiley:
New York, 1985; pp 664–666; Bernasconi, C. F.; Tetrahe-
dron 1989, 45, 4017.
6. Becker, K. B.; Boschung, A. F.; Geisel, M.; Grob, C. A. Helv.
Chim. Acta 1973, 56, 2747.
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