Org. Synth. 1953, 33, 72
DOI: 10.15227/orgsyn.033.0072
4-PHENYL-m-DIOXANE
[m-Dioxane, 4-phenyl-]
Submitted by R. L. Shriner and Philip R. Ruby
1.
Checked by Richard T. Arnold, W. E. Parham, and John E. Franz.
1. Procedure
In a 2-l. round-bottomed flask, fitted with a reflux condenser and mechanical stirrer, are placed 675 g. (8.3 moles) of 37% formalin, 48 g. of sulfuric acid (sp. gr. 1.84), and 312 g. (3 moles) of styrene. The resulting mixture is gently refluxed and stirred for 7 hours. The mixture is cooled, and 500 ml. of benzene is stirred in. The layers are separated, and the aqueous layer is extracted with 500 ml. of benzene. The benzene solutions are combined and washed with two 750-ml. portions of water. The benzene is removed by distillation, and the residual liquid is fractionated under reduced pressure. At 2 mm. pressure a forerun is collected separately, up to a temperature of 96° (Note 1); then the main fraction is collected at 96–103°/2 mm. The yield of 4-phenyl-m-dioxane amounts to 353–436 g. (72–88%): n20D 1.5300–1.5311: d204 1.092–1.093 (Note 2).
2. Notes
1.
The amount of fore-run and the yield depend on the efficiency of the fractionation. With a 7-cm. distilling head, a fore-run of
75 g. boiling at
84–96°/2 mm. was collected, whereas with a heated
Vigreux column (2 cm. by 35 cm.) the fore-run amounted to only
11 g. and the higher yields were obtained. The fore-run may be refractionated to obtain additional product. The checkers used a
2 cm. by 20 cm. column packed with stainless-steel helices, and collected their product (
72–75% yield) over a 1° boiling range (94–95°/2 mm.,
n20D 1.5300).
2.
This modification of the Prins
2 reaction has been applied to other olefins.
3 The aryl olefins give the best yields; see the tabulation.
|
|
Aryl Olefin
|
Yield of Substituted m-Dioxane, %
|
|
|
α-Methylstyrene
|
58
|
|
Propenylbenzene
|
66
|
|
Anethole
|
89
|
|
Isosafrole
|
84
|
|
1-(3',4'-Dimethoxyphenyl)-1-propene
|
68
|
|
1-(p-Cumyl)-1-propene
|
96
|
|
3. Discussion
4-Phenyl-m-dioxane was obtained by Prins
2 by the reaction between
styrene and
formaldehyde in the presence of
sulfuric acid. The correct structure was pointed out by Fourneau, Benoit, and Firmenich.
4 The above procedure is essentially that given by Shortridge
5 and by Beets
3 and mentioned in a patent.
6 Methylphenylcarbinol has been substituted for
styrene.
3
This preparation is referenced from:
Appendix
Chemical Abstracts Nomenclature (Collective Index Number);
(Registry Number)
1-(p-Cumyl)-1-propene
sulfuric acid (7664-93-9)
Benzene (71-43-2)
formaldehyde,
formalin (50-00-0)
styrene (100-42-5)
methylphenylcarbinol (98-85-1)
propenylbenzene
isosafrole (120-58-1)
α-methylstyrene (98-83-9)
Anethole (104-46-1)
m-Dioxane (505-22-6)
4-Phenyl-m-dioxane,
m-Dioxane, 4-phenyl- (3141-24-0)
1-(3',4'-Dimethoxyphenyl)-1-propene
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