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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. Ruby1.
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 Prins2 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 Prins2 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 Shortridge5 and by Beets3 and mentioned in a patent.6 Methylphenylcarbinol has been substituted for styrene.3
This preparation is referenced from:

References and Notes
  1. State University of Iowa, Iowa City, Iowa.
  2. Prins, Chem. Weekblad, 14, 932 (1917); 16, 1072, 1510 (1919); Proc. Acad. Sci. Amsterdam, 22, 51 (1919).
  3. Beets, Rec. trav. chim., 70, 20 (1951); Beets and Van Essen, Rec. trav. chim., 70, 25 (1951); Drukker and Beets, Rec. trav. chim., 70, 29 (1951).
  4. Fourneau, Benoit, and Firmenich, Bull. soc. chim. France, 47, 858 (1930).
  5. Shortridge, J. Am. Chem. Soc., 70, 873 (1948).
  6. Engel, U. S. pat. 2,417,548 [C. A., 41, 3493 (1947)].

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