Diels Alder Results

O toluene O + O reflux O
Source Diels,O.; Alder, K. Chem. Ber. 1929 J. Am. Chem. Soc. 1984 J.Chem. Ed. Dictionary of Organic Compounds Multiscale Operational Organic Chemistry Organic Chemistry Laboratory Experiments and Techniques (U of U) Edited? Peer edited Peer edited Peer edited Data taken from primary literature 3 editors No editor/outside review 80-81 80-82 oC 81 o 108 oC

O O O
Endo mp (oC)

O O O
Exo mp (oC) 125 oC 124-125 oC 114 125-126 114

Electrophilic Aromatic Substitution

Nitration of Toluene

I. Electrophilic Aromatic Substitution

In general:
H H H H H E+ H H H H H H E H+

An example:
H H H H H Br Br H FeBr3 H H H H Br HBr H FeBr3

II. Basic Mechanism

H H H H H Br Br H FeBr3

http://www.cem.msu.edu/~reusch/VirtualText/benzrx1.htm

III. Directing Groups

Y E Y E Y E Y E

IV.

Why are some Y groups ortho/para directors and others meta directors?
H H OCH3 H Br H H

H H

OCH3 H H H

Br Br

FeBr3

H H

OCH3 H H Br H

H H

OCH3 H H Br H

V. This weeks lab

H3C H2SO4, HNO3 A O2N H3C H3C NO2 H3C NO2

dinitrated products

Attempt mechanism leading to para substituted product before coming to lab. Also include formation of activated electrophile. Predict which will be major product(s) (ortho, meta, and or para) and explain your reasoning. Predict whether the nitro group is activating or deactivating. Do you predict Reaction A or B above will proceed at a higher rate? Do you expect that the mono- or di-nitrated products will be formed in greater amounts?

VI. Procedural Modifications

1) 2) 3) 4) 5) 6) 7) 8) Double nitric acid only Double sulfuric acid only Double both acids Lower reaction temperature 10 degrees Double reaction time Lower reaction temp 10 degrees and double reaction time Do not raise reaction temperature (or some TNT may form) Other possibilities not excluded

VII. Analysis of Products Gas Chromatography

http://www.chem.vt.edu/chem-ed/sep/gc/gc.html

VIII. Sample Calculations

IX. SAFETY
Concentrated nitric acid: strong oxidizer. Incompatible with a large number of compounds please measure only what they need directly from the bottle. Nitric acid reacts violently with acetone. Do NOT wash glassware with acetone before lab. Be sure any nitric acid waste is disposed of in INORGANIC WASTE. Conc. Nitric and sulfuric can cause severe burns. Goggles required at all times. Gloves and long sleeved shirt strongly recommended. Be VERY careful handling bottles, re-cap as soon as your are finished and clean up spills as soon as they occur especially in the common hood. 90% of the lab injuries that I have witnessed have been acid burns during this experiment. If you get some acid on you, remove the affected clothing immediately and rinse with water for at least 15 minutes.

X. Procedural Tips
Be sure to pre-mix nitric and sulfuric acids well. Allow time to react. Why? It is important all samples be dried thoroughly before they are injected on the gc. Water is incompatible with the column. How can you tell if your sample is dry? Before injecting samples in the gc, dilute 1 drop of the product in 5 drops of diethyl ether

XI. Before you leave lab

Obtain GC for your product mixture. Calculate the percentage of each compound present in your product mixture. Write your results on the board. Write down your classmates results so that you may incorporate their data into your conclusion. Clean up your area