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Org. Synth. 1951, 31, 104
DOI: 10.15227/orgsyn.031.0104
TETRAPHENYLETHYLENE
[Ethylene, tetraphenyl-]
Submitted by Robert E. Buckles and George M. Matlack1.
Checked by T. L. Cairns and C. J. Albisetti.
1. Procedure
A solution of 75 g. (0.32 mole) of diphenyldichloromethane (Note 1) in 250 ml. of anhydrous benzene is placed in a 500-ml. round-bottomed flask fitted with a reflux condenser. To the solution is added 50 g. (0.78 g. atom) of powdered copper (Note 2). The mixture is boiled gently for 3 hours. The hot solution is filtered, and 250 ml. of absolute ethanol is added to the filtrate. On cooling 25–31 g. (47–60%) of light yellow crystals, m.p. 222–224°, are obtained. The mother liquor is concentrated to about 200 ml. by distillation from a 1-l. Claisen flask. Cooling the residue yields 6–12 g. of yellow product. Crystallization of this crude material from a 1:1 by volume mixture (12 ml. for each gram) of absolute ethanol and benzene gives an additional 2.5–10 g. of tetraphenylethylene, m.p. 223–224°. The total yield is 29–37 g. (55–70%).
2. Notes
1. Diphenyldichloromethane is conveniently prepared from benzophenone and phosphorus pentachloride.2 A product of b.p. 180–181°/17 mm. is obtained in about 90% yield.
2. The checkers used bronze powder obtained from George Benda, Inc., Boonton, New Jersey. Some varieties of copper powder tended to form a dense paste which did not disperse readily and resulted in lower yields.
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3. Discussion
This procedure is adapted from the method of Schlenk and Bergmann.3 Tetraphenylethylene has been prepared by the reaction of diphenylmethane with diphenyldichloromethane;4 by the reaction of diphenyldichloromethane with silver or zinc;4 by the reaction of thiobenzophenone with copper;5 by the reaction of diphenylmethane with sulfur;6 by the reduction of benzophenone with amalgamated zinc in the presence of hydrochloric acid;7 by the rearrangement of 1,2,2,2-tetraphenylethanol with acetyl chloride;8 by the reaction of diphenylmethane with bromine, followed by treatment of the product with sodium iodide in acetone;9 by the reaction of 1,2-difluoro-1,2-diphenylethylene with phenyllithium;10 by the reaction of diphenylchloromethane with sodium or potassium amide in liquid ammonia;11 and by treatment of 2,2,3,3-tetraphenylpropionitrile with potassium amide in liquid ammonia.12

References and Notes
  1. State University of Iowa, Iowa City, Iowa.
  2. Org. Syntheses Coll. Vol. 2, 573 (1943).
  3. Schlenk and Bergmann, Ann., 463, 1 (1928).
  4. Norris, Thomas, and Brown, Ber., 43, 2958 (1910).
  5. Schönberg, Shütz, and Nickel, Ber., 61, 1375 (1928).
  6. Ziegler, Ber., 21, 779 (1888); Moreau, Bull. soc. chim. France, 1955, 628.
  7. Steinkopf and Wolfram, Ann., 430, 113 (1923).
  8. Lévy and Lagrave, Bull. soc. chim. France, [4] 43, 437 (1928).
  9. Gorvin, J. Chem. Soc., 1959, 678.
  10. Dixon, J. Org. Chem., 21, 400 (1956).
  11. Hauser, Brasen, Skell, Kantor, and Brodhag, J. Am. Chem. Soc., 78, 1653 (1956).
  12. Hauser and Brasen, J. Am. Chem. Soc., 78, 82 (1956).

Appendix
Chemical Abstracts Nomenclature (Collective Index Number);
(Registry Number)

amalgamated zinc

sodium or potassium amide

ethanol (64-17-5)

hydrochloric acid (7647-01-0)

ammonia (7664-41-7)

Benzene (71-43-2)

phosphorus pentachloride (10026-13-8)

acetyl chloride (75-36-5)

bromine (7726-95-6)

sulfur (7704-34-9)

copper,
copper powder (7440-50-8)

acetone (67-64-1)

Benzophenone (119-61-9)

zinc (7440-66-6)

diphenyldichloromethane (2051-90-3)

Diphenylmethane (101-81-5)

sodium iodide (7681-82-5)

Phenyllithium (591-51-5)

silver (7440-22-4)

Thiobenzophenone (1450-31-3)

potassium amide

Tetraphenylethylene,
Ethylene, tetraphenyl- (632-51-9)

1,2,2,2-tetraphenylethanol

1,2-difluoro-1,2-diphenylethylene

diphenylchloromethane (90-99-3)

2,2,3,3-tetraphenylpropionitrile

Notes

1. Diphenyldichloromethane is conveniently prepared from benzophenone and phosphorus pentachloride.2 A product of b.p. 180–181°/17 mm. is obtained in about 90% yield.

2. The checkers used bronze powder obtained from George Benda, Inc., Boonton, New Jersey. Some varieties of copper powder tended to form a dense paste which did not disperse readily and resulted in lower yields.

References/EndNotes

Article Compounds

Authors