Aldol Condensation Diels-Alder Name: John OConnor Lab: F 8:00 a.m.

. 420 CE Teaching Assistant: Emily Vojt Submitted: March 22, 2013

Purpose: To synthesize 2,3,4,5-tetraphenylcyclopentadienone from benzil and dibenzyl ketone via an aldol concentration reaction and use the resulting product along with isoamyl nitrite and anthranilic acid to synthesize 1,2,3,4tetraphenylnaphthalene via a Diels-Alder reaction. Reaction Scheme (aldol condensation):

Synthesis of 2,3,4,5-tetraphenylcyclopentadienone:1 A solution of benzil (1.9643 g, 9.3436 mmol), dibenzyl ketone (1.6710 g, 7.9469 mmol), and anhydrous ethanol (15 mL) was heated at 70 C under a reflux condenser for five minutes. A solution of potassium hydroxide (0.5 g) and anhydrous ethanol (5 mL) was added to the benzil solution in two equal portions, and the solution was heated for 15 minutes at 78 C. The product was crystallized out of solution by cooling to 0 C. The suspension was vacuum filtered, resulting in a deep purple crystalline product, 2,3,4,5-tetraphenylnaphthalene (2.4511 g, 6.3753 mmol, 80%): mp 218-219 C (lit2 mp 219-220 C).

Reaction Scheme (Diels-Alder):

Synthesis of 1,2,3,4-tetraphenylnaphthalene:3 A solution of tetraphenylcyclopentadienone (0.9460 g, 2.461 mmol) and dimethoxyethane (7.5 mL) was heated to 85 C with a reflux condenser attached. While refluxing, a solution of anthranilic acid (0.3761 g, 2.743 mmol) and dimethoxyethane (3.5 mL) was added through a Claisen adapter simultaneously with a solution of isoamyl nitrite (0.463 g, 0.500 mL, 3.72 mmol) and dimethoxyethane (3.5 mL) added through the reflux condenser. The two solutions were added in .1 mL portions over 45 minutes, and the reaction refluxed at 85 C for an additional 15 minutes. The suspension was evaporated using a rotovap, and the resulting solid crude product was triturated in methanol. The product was vacuum filtered, resulting in a white-yellow powder product, 1,2,3,4tetraphenylnaphthalene (0.8364 g, 1.934 mmol, 79%): mp 202-204 C (lit4 mp 196199 C or 203-205 C). Discussion: The synthesis of 1,2,3,4-tetraphenylnaphthalene was accomplished through a twostep procedure. In the first part of the procedure, benzil and dibenzyl ketone were reacted in ethanol in the presence of a basic catalyst, KOH, to yield 2,3,4,5tetraphenylcyclopentadienone as a purple crystalline solid in 80% yield. The melting point range of the product was determined to be 218-219 C, which borders the reported literature range and supports the identity of the product as 2,3,4,5tetraphenylcyclopentadienone. The narrow melting point range indicates the product is relatively free of impurities. In the second part of the procedure, anthranilic acid, and isoamyl nitrite were reacted in dimethoxyethane to generate

benzyne in situ. Benzyne then reacted with 2,3,4,5-tetraphenylcyclopentadienone to yield 1,2,3,4-tetraphenylnaphthalene as a white-yellow powder solid in 79% yield. The melting point range of the product was determined to be 202-204 C, which is partially within the reported literature range and supports the identity of the product as 1,2,3,4-tetraphenylnaphthalene. The narrow melting point range indicates the product is relatively free of impurities. The aldol reaction in the first step produced only one product in significant yield for two reasons. First, benzils lack of an alpha proton prevents it from forming an enolate, therefore all enolate formation was by dibenzyl ketone. Second, the dibenzyl ketone enolate was not very prone to self-condensation due to the benzil carbonyl groups being more electrophilic. Yield for this step could have been improved by generating the product through the reaction of 1,2,3,4-tetraphenyl-1,4-dilithio-1,3-diene and carbon dioxide. This reaction possesses two advantages. While side product generation was minimized in the aldol condensation, this procedure offers even more negligible side product generation. Also, this reaction is not an equilibrium reaction, so unreacted products are less prevalent5. In step two, anthranilic acid and isoamyl nitrite were added in small simultaneous quantities because benzyne readily dimerizes. In order to minimize benzyne dimerization, it needed to be present in much smaller quantities than 2,3,4,5-tetraphenylcyclopentadienone. As the cyclopentadienone reactant was used up, additional benzyne was more likely to dimerize. Therefore, yield could have been improved by using benzyne (either anthranilic acid or isoamyl nitrite) as the limiting reagent, rather than 1,2,3,4cyclopentadienone. References: (1) Callam, C.S.; Paul, N.M. Aldol Condensation. Chemistry 2550 Organic Chemistry Lab 2012 Academic Year, McGraw-Hill: United States, 2012; pp 113-114 (2) Sigma-Aldrich Chemical Catalog Online, http://www.sigmaaldrich.com/unitedstates.html (accessed Feb 2013); Search: Product No. T25801 (3) Callam, C.S.; Paul, N.M. Diels Alder. Chemistry 2550 Organic Chemistry Lab 2012 Academic Year, McGraw-Hill: United States, 2012; pp 122-124 (4) Sigma-Aldrich Chemical Catalog Online, http://www.sigmaaldrich.com/unitedstates.html (accessed Feb 2013); Search: Product No. 149799 (5) Xi, Z.; Song, Q. Efficient Synthesis of Cyclopentadienone Derivatives by the Reaction of Carbon Dioxide with 1,4-Dilithio-1,3-dienes. Journal of Organic Chemistry. 2000. 65 (260). 9157-9159.