Organic Syntheses, CV 4, 375
Submitted by Donald J. Reif and Herbert O. House
1.
Checked by M. S. Newman and W. H. Powell.
1. Procedure
In a
1-l. separatory funnel is placed a solution of
39.2 g. (0.2 mole) of trans-stilbene oxide (Note
1) in
450 ml. of reagent benzene. To the solution is added
13.2 ml. (0.1 mole) of boron trifluoride etherate (Note
2). The solution is swirled, allowed to stand for 1 minute (Note
3), and then washed with two 300-ml. portions of water. The organic layer is separated, and the
benzene is removed by distillation (Note
4). The residual crude aldehyde is purified by distillation under reduced pressure. The product, collected at
115–117°/0.6 mm., amounts to
29–32 g. (
74–82%),
nD25 1.5875–1.5877 (Note
5).
2. Notes
2. A
practical grade of boron trifluoride etherate, purchased from Eastman Kodak Company, was redistilled before use. The pure etherate boils at
126°.
3. Discussion
Diphenylacetaldehyde has been prepared by the isomerization of
1,2-dihydroxy-1,2-diphenylethane either thermally
3 or in the presence of
sulfuric acid,
4,5,6 oxalic acid,
7 or
acetic anhydride.
8 The aldehyde has also been produced by the reaction of
2,2-dipheny1-2-hydroxyethyl ether with
sulfuric acid6,7 or
oxalic acid;
7,9 by the reaction of
hydrochloric acid with
2-amino-1,1-diphenylethanol;
10 by the reaction of hydrobromic
11 or hydrochloric
12 acid with
2-diethylamino-1,1-diphenylethanol; by the hydrolysis of
β,β-diphenylvinyl ethyl ether;
13 by the thermal rearrangement of
deoxybenzion;
14 by the hydrolysis and decarboxylation of the glycidic ester obtained from
ethyl chloroacetate and
benzophenone;
15 by passing a mixture of
diphenylacetic and formic acid over
thorium oxide on
pumice at 450°;
16 and by the hydrolysis of
diphenylacetaldehyde enol methyl ether (obtained from
benzophenone and
methoxymethylenetriphenylphosphorane).
17
This preparation is referenced from:
Appendix
Compounds Referenced (Chemical Abstracts Registry Number)
2,4-dinitrophenylhydrazone
2,2-dipheny1-2-hydroxyethyl ether
deoxybenzion
diphenylacetic and formic acid
pumice
diphenylacetaldehyde enol methyl ether
Diphenylactaldehyde
cis- or trans-stilbene oxide
sulfuric acid (7664-93-9)
hydrochloric acid (7647-01-0)
Benzene (71-43-2)
acetic anhydride (108-24-7)
Oxalic acid (144-62-7)
sodium bisulfite (7631-90-5)
thorium oxide
carbon (7782-42-5)
Benzophenone (119-61-9)
oxirane (75-21-8)
ethylene (9002-88-4)
Ethyl chloroacetate (105-39-5)
magnesium sulfate (7487-88-9)
2,4-Dinitrophenylhydrazine (119-26-6)
stilbene
Diphenylacetaldehyde,
Acetaldehyde, diphenyl- (947-91-1)
boron trifluoride etherate,
boron trifluride etherate (109-63-7)
1,2-dihydroxy-1,2-diphenylethane
2-amino-1,1-diphenylethanol
2-diethylamino-1,1-diphenylethanol
β,β-diphenylvinyl ethyl ether
methoxymethylenetriphenylphosphorane
lithium diethylamide
carbon-carbon
trans-Stilbene oxide (1439-07-2)
trans-Stilbene (103-30-0)
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