Org. Synth. 1965, 45, 89
DOI: 10.15227/orgsyn.045.0089
PHENYL t-BUTYL ETHER
[Ether, tert-butyl phenyl]
[Method I]
Submitted by Christer Frisell and Sven-Olov Lawesson
1.
Checked by William G. Dauben and Gilbert H. Berezin..
1. Procedure
A 1-l., three-necked, round-bottomed flask equipped with a sealed mechanical stirrer, a reflux condenser, and a 500-ml. pressure-equalized dropping funnel is arranged for conducting a reaction in an atmosphere of nitrogen by fitting into the top of the condenser a T-tube attached to a low-pressure supply of nitrogen and to a mercury bubbler. The flask is dried by warming with a soft flame as a slow stream of nitrogen is passed through the system. In the cooled flask a solution of phenylmagnesium bromide is prepared from 13 g. (0.53 g. atom) of magnesium turnings, 79 g. (0.5 mole, 53.6 ml.) of bromobenzene, and 200 ml. of anhydrous ether.
After the preparation of phenylmagnesium bromide is complete, the ethereal solution is cooled in an ice bath and 200 ml. of anhydrous ether is added. A solution of 58.3 g. (0.3 mole, 56 ml.) of t-butyl perbenzoate (Note 1) in 120 ml. of anhydrous ether is added, dropwise, with stirring over a 30-minute period, and the stirring is continued for an additional 5 minutes.
The reaction mixture is poured carefully into a cold solution of 40 ml. of concentrated hydrochloric acid in 1 1. of water. The ethereal layer is separated, and the aqueous layer is extracted twice with 150-ml. portions of ether. The combined organic layers are extracted with three 25-ml. portions of 2M sodium hydroxide solution, washed with water until the washings are neutral, and then dried over anhydrous magnesium sulfate (Note 2) and (Note 3). The dried solution is concentrated and the product distilled under reduced pressure, b.p. 57–59°/7 mm. The yield of phenyl t-butyl ether is 35–38 g. (78–84%), n25D 1.4870–1.4880. This synthetic process is applicable to the preparation of other t-butyl ethers (Note 4).
2. Notes
1.
t-Butyl perbenzoate is supplied by Lucidol Division, Wallace and Tiernan Inc., Buffalo 5, New York, or L. Light & Co., Ltd., Colnbrook, Bucks, England. The Lucidol product contains
98% t-butyl perbenzoate.
2.
The ethereal solution should be tested for peroxides as follows: A few milligrams of
sodium iodide, a trace of
ferric chloride, and
3 ml. of glacial acetic acid are placed in a test tube and
2 ml. of the ether solution added carefully. When unconsumed perbenzoate is present, a yellow ring is formed immediately between the two phases. If a positive test is obtained, the acid and base treatments should be repeated.
3.
By acidification of the
sodium hydroxide solution,
29–32 g. of
benzoic acid (
80–90%) is obtained.
4.
The same general method
2 has been used by the submitters to prepare
o-tolyl t-butyl ether,
3 m-tolyl t-butyl ether,
3 benzyl t-butyl ether,
3 and
p-anisyl t-butyl ether.
3. Discussion
The method presented is essentially that described by Lawesson and Yang.
4 Phenyl t-butyl ether has been prepared by acid-catalyzed condensation of
isobutylene and
phenol5 by reaction of
diphenyliodonium chloride with
potassium t-butoxide,
6 and by the next procedure in this volume.
74. Merits of Preparation
The synthesis of t-butyl ethers by the reaction of Grignard reagents with t-butyl perbenzoate appears to have considerable generality (Note 4), and the perester is a stable, readily available material.
This preparation is referenced from:
Appendix
Chemical Abstracts Nomenclature (Collective Index Number);
(Registry Number)
t-butyl perbenzoate
hydrochloric acid (7647-01-0)
acetic acid (64-19-7)
ether (60-29-7)
sodium hydroxide (1310-73-2)
magnesium turnings (7439-95-4)
phenol (108-95-2)
nitrogen (7727-37-9)
Benzoic acid (65-85-0)
bromobenzene (108-86-1)
ferric chloride (7705-08-0)
Phenylmagnesium bromide (100-58-3)
sodium iodide (7681-82-5)
magnesium sulfate (7487-88-9)
isobutylene (9003-27-4)
diphenyliodonium chloride (1483-72-3)
potassium t-butoxide (865-47-4)
m-tolyl t-butyl ether
benzyl t-butyl ether
PHENYL t-BUTYL ETHER,
Ether, tert-butyl phenyl (6669-13-2)
o-tolyl t-butyl ether (15359-96-3)
p-anisyl t-butyl ether (15360-00-6)
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