A Useful Grignard Reaction: The Synthesis of Dyes

Chemistry 223L

Objective: To synthesize and use two dyes, malachite green and crystal violet, prepared from 4-bromo-
N,N-dimethylaniline.

Background: Organometallic compounds are compounds that contain carbon-metal bonds. Grignard
reagents, RMgX, are among the most versatile organic chemistry reagents. They are formed by rapidly
stirring the corresponding alkyl halide with suspensions of magnesium metal.

Mg
R X R Mg X
Once formed, Grignard reagents can undergo a variety of reactions. In todays lab, the Grignard reagent
will attack the center of positive charge in a second molecule to create a new carbon-carbon bond. Note
that Grignard reagents will also react with any water present. This reaction with water will result in a low
yield of the desired product so it is essential to use glassware and solvent that has been scrupulously dried.

NOTE 1: The products stain readily. Wear gloves, old clothes, and try to be neat. The desired products are
also somewhat toxic. Minimize direct contact.

NOTE 2: At least a day before performing this lab, place a 250 mL round-bottom flask, a 100 mL graduated
cylinder and a reflux condenser in the oven to ensure that it is dry when you begin the lab.

Mechanism:

N N O O-
O
Mg
O O O O
O

Br MgBr N

A A
N

O-
O O-
A
O
N N N N N N

HCl

OH2+ Cl- N N

N N

N
N
+ Cl-

Crystal Violet
 O- O
O BrMg N O
O
A N

A
N

N OH 2+ O-

HCl
N N

N Cl - N N

Malachite Green

Procedure: Students will work in teams of two. One member of the team will synthesize Crystal Violet and
the other will synthesize Malachite Green. The team will share their products to tie-dye.

Crystal Violet: Assemble the flask and condenser in the hood. (Caution: hot glass looks the same as cold
glass!) Stopper the second joint of the flask. Add 0.40g Mg and 23 mL of anhydrous THF to the flask. Add
2.5. g 4-bromodimethylaniline and one small iodine crystal to the flask. Gently warm the flask to reflux and
maintain the reflux for 30 minutes. During this time the solution should change from dark to dingy gray.
Use an ice bath to cool the flask to room temperature and add a solution of 0.25g diethyl carbonate
in 2.5 mL anhydrous THF. Return to reflux for 5 minutes and again cool to room temperature with an ice
bath.
Slowly add 8 mL of 10% HCl (the reaction will be vigorous) to get the desired product. The result
will be a muddy purple solution.

Malachite Green: Follow the above procedure but add 0.43 g methyl benzoate in place of diethyl
carbonate.

TIE DYE: Each student will be given cotton cloth to dye. Simply dip the cloth in the final solution for 1
minute and then rinse under running water. After rinsing the excess dye from the material, place it on a pad
of newspaper to dry and fill out a label to attach to the cloth. Twisting cloth and using multiple dyes will
afford nice patterns, which may be displayed in the glass cases of Salem Hall.

Waste: All dye mixtures and any excess THF should be placed in the labeled waste bottle in the hood.

Reference: Taber, D.F.; Meagley, R. P.; Supplee, D. J.; J. Chem Ed., 73, 259-260, 1996.

Postlab Questions

1. Draw a mechanism showing why water should not be allowed to come in contact with the Grignard
reagent.
2. Why is the solution cooled before adding the 10% HCl solution?