Chlorination of 2-tert-butylphenol; 2-tert-butyl-4-chlorophenol
SyntheticPage 672
DOI:
10.1039/SP672
Submitted Jul 26, 2013, published Aug 29, 2013
Chemicals Used
2-tert-butylphenol (Aldrich)
Diphenylsulfide (Aldrich)
Aluminium trichloride (Aldrich)
Sulfuryl chloride (Aldrich)
Procedure
Diphenylsulfide (0.09 ml, 0.10 g, 0.54 mmol) and AlCl3 (0.10 g, 0.75 mmol) were dissolved in 2-tert-butylphenol (15.35 ml, 15.02 g, 0.10 mol) in a three neck round bottom flask, under nitrogen flow. The flask outlet was fitted with a sat. NaOH(aq) scrubber. The solution was cooled in an ice bath, and sulfuryl chloride (7.97 ml, 13.4 g, 0.10 mol) was added dropwise over ca 40 min. The solution became yellow, then red, and was stirred at ambient temperature overnight. The solution was concentrated and purified by vacuum distillation using a 12 cm Vigreux column. Fraction results summarised below.
|
Fraction
|
Stillhead temperature
|
Heating block temperature
|
r.f (hexane / diethyl ether 20:1)
|
Assignment by 1H NMR
|
|
1
|
40-46
|
60-110
|
0.41
|
ortho
|
|
2
|
50-80
|
120-170
|
0.12/0.41
|
mixture
|
|
3
|
80-90
|
180-190
|
0.12
|
para
|
All products were clear oils. Fraction 2 was further purified by column chromatography (hexane/diethyl ether 20:1). Overall yield of ortho isomer = 7.49 g, 40 %; para isomer = 9.40 g, 51 %.
Author's Comments
Worked well however this reaction is not selective and will give you the ortho and para isomer. The NMR spectrum for the para isomer is below
Data
1H NMR (400 MHz, CDCl3): 7.22 (1H, d, 4J = 2 Hz, Hc), 7.02 (1H, dd, 4J = 2 Hz, 3J = 8 Hz, Hb), 6.59 (1H, d, 3J = 8 Hz, Ha), 4.78 (1H, s, OH), 1.39 (9H, s, tBu).
Lead Reference
G. W. Theaker, C. Morton and P. Scott, Dalton Trans., 2008, 6883-6885. http://dx.doi.org/10.1039/b818829g
Other References
W. D. Watson, J. Org. Chem., 1985, 50, 2145-2148.
http://dx.doi.org/10.1021/jo00212a029
Supplementary Information
1H NMR (1H NMR.jcamp)
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Keywords: addition, alcohols, aromatics/arenes, chlorination, electrophilic, sulphides
