FREE RADICAL HALOGENATION CONVERSION OF CYCLOHEXANE INTO CHLOROCYCLOHEXANE This experiment is a modification of one within Roberts et al, Modern

Experimental Organic Chemistry, Saunders College. OBJECTIVES: 1. To demonstrate a free radical substitution reaction by converting cyclohexane into chlorocyclohexane. 2. To learn reflux technique. 3. To compare the simple distillation of a homogeneous system to the previously performed heterogeneous system. BACKGROUND: The underlying concepts and mechanisms for free radical substitution reactions will be covered in lecture and can be found in Wade. The alkane to be monochlorinated is cyclohexane. The molecule possesses a six fold symmetry, so all of its 12 hydrogens are equivalent. Therefore, substitution of any 1 hydrogen will lead to the same product, chlorocyclohexane. The chlorinating reagent, sulfuryl chloride (SO2Cl2) is preferred over Cl2 gas because as a liquid, it is easier and safer to work with (see safety note). Light, the initiating agent with Cl2, does not work with sulfuryl chloride, instead, azobisisobutyronitrile (AIBN) will play that role. hv Initiation with Cl2: Cl-Cl ----> 2 Cl. Initiation with AIBN: heat . (CH3)2C(CN)-N=N-C(CN)(CH3)2 -----> N2 + 2 (CH3)2C-CN . (CH3)2C-CN + Cl-SO2-Cl -----> (CH3)2C(CN)Cl + .SO2Cl

.SO Cl -----> SO2(g) + Cl. 2 unstable toxic --------------------------------------------------------------------*Sulfuryl chloride can be found in the CRC Handbook of Chemistry & Physics in the Table of Inorganic Compounds. Heating AIBN promotes a homolytic cleavage which releases very stable nitrogen gas (N2). The remaining carbon portion is a reactive radical which quickly abstracts a Cl atom from the sulfuryl chloride. The sulfuryl chloride radical is unstable and dissociates into toxic SO2 and a free Cl. radical. This Cl. begins the propagation steps. The source of the chlorine for the chain propagation is again sulfuryl chloride and not chlorine gas. The combining of any two radicals will lead to termination of the chain sequence. Obviously, exhaustion of the starting materials (cyclohexane and sulfuryl chloride) will also terminate the reaction. Since the homolytic cleavage of AIBN requires heating, the reaction mixture is refluxed. Reflux is a technique that provides activation energy and increases the rate of reaction. It does so by heating the system, but preventing evaporation of reagents and solvents by trapping escaping vapors in a water-jacketed condenser. The vapors are reliquified by the circulating cold water and drip back into the reaction flask. Toxic sulfur dioxide and hydrogen chloride are produced, and will be gaseous even at cold water temperature necessitating that the reaction be performed in the hood. One mole of SO2 and HCl are lost for every mole of product produced. Calculation of the moles of chlorocyclohexane to be produced also gives the moles

-2of SO2 and HCl lost. Moles can be converted into grams. Therefore, the completion of the reaction can be monitored by weighing the reaction flask.

Propagation:

Cl

+ . +

HCl (g) toxic

Cl ClSO2Cl
.

+ SO2 +

SO2Cl

SO2Cl

Purification Extraction and Drying: When the theoretical amount of mass is lost, the reaction is over. The desired product must be separated from unreacted reagents and byproducts. First, SO2Cl2 is easily disposed of by pouring the reaction mixture into ice water. The water reacts with the SO2Cl2 and the toxic gases produced remain dissolved. Again for obvious reasons this quenching step will be performed in the hood. Ice water is used to keep this exothermic quenching reaction under control. Unreacted cyclohexane and water still need to be separated from chlorocyclohexane. As cyclohexane and chlorocyclohexane are non-polar substances, and water is polar, they are not miscible. At the end of the ice water quench, there should be two layers in the beaker. Physical separation of the two layers is easily accomplished using a separatory funnel. The denser bottom layer is drained through the stopcock and the remaining layer is poured out through the top. Even though the bulk of the acidic water (dissolved SO2 and HCl) can be drained away, the organic layer is coated with trace acid. This necessitates the washing of the organic layer with dilute aqueous bicarbonate to neutralize the acid. Carbon dioxide gas is liberated during this process so the funnel must be frequently vented and pointed to the back of the hood. After the aqueous carbonate wash, the organic layer is coated with water. This trace amount of water can be removed by mixing the organic layer with drying agent. Purification - Simple Distillation: At this point, all reagents and side products have been cleaned away from the product except unreacted cyclohexane (and polychlorinated alkane?). In order to isolate the chlorocyclohexane from cyclohexane, a physical property will be advantageously manipulated. The boiling points for the two compounds differ by 600C. The difference is large enough for a simple distillation to successfully separate the components. Analysis: Once the distillation is over, an identity and purity check of the two fractions must be performed. Besides the boiling point obtained during distillation, the more sensitive refractive index will be measured. Since refraction is a temperature dependent function, remember to include a temperature correction of 0.00045/0C deviation from the reported literature value. SAFETY: 1. SO2Cl2 is highly corrosive and reacts violently with water. Even air moisture destroys the reagent producing noxious SO2 and HCl gases. Your instructor will dispense the SO2Cl2 from a ventilation hood. Wear plastic disposable gloves when

Cl. chain continues

-3receiving and working with reagent. Make sure round bottom flask is dry and properly stoppered. 2. AIBN is shock sensitive and can explode. Do not mistreat reagent bottle. Keep acetone and metals away from AIBN. 3. Check all glassware for star cracks or chips before using. 4. Cyclohexane and chlorocyclohexane are flammable. Use a heating mantle and variac as heat source, not an open flame. 5. During the extraction with aqueous sodium carbonate, CO2 gas is liberated. Frequently vent separatory funnel after gently shaking it. EXPERIMENTAL PROCEDURE: week 1: Free Radical Chlorination and Initial Isolation of Product

From the stockroom: 250-ml heating mantle & 125-ml separatory funnel. Gather a DRY 250-ml RBF with stopper, 400-ml beaker, condenser, one clamp and variac. Seat your RBF in the beaker while you amass all reagents and weights. Measure out 25.0 ml of cyclohexane and place it in the RBF. Wearing disposable plastic gloves proceed to your instructor with the stoppered RBF to receive 9.0 ml of SO2Cl2. Next weigh out 0.10g of AIBN in a plastic tub (do not use metal spatula) and add it to the RBF in the hood. Obtain the total mass of the stoppered RBF as it sits in the beaker. Move to a hood and set-up a reflux assembly. Do not start heating reaction until reflux assembly has been checked by instructor. Once your set-up has passed inspection, reflux for 20 minutes (50 volts). (The reflux period is counted from the point of boiling with returning condensate.) Cool the reaction flask with tap water, dry and reweigh it. If the loss of mass is less than theoretical, add another small portion of AIBN and reflux for 10 minutes more. After the theoretical amount of mass has been lost, return to a hood and cautiously pour the reaction mixture into 25.0 ml of ice water. Transfer the resulting two-phase solution to a 125-ml separatory funnel. If separation into two layers does not occur readily, add some sodium chloride to the funnel and shake. Separate the two layers. (How do you know which layer is the organic and which is the aqueous?) Wash the organic layer containing the cyclohexane and chlorocyclohexane with multiple 10-ml portions of aqueous 0.5M sodium carbonate until the aqueous layer remains basic to litmus paper. Next wash the organic layer with 10-ml of fresh water. Transfer the organic layer to your 125-ml E. flask and add 3g of CaCl2. Stopper the flask, wrap its neck with parafilm and store it safely away seated in a labeled beaker until next period. The aqueous washes can now be poured down the sink. week 2: Distillation of Chlorocyclohexane from Unreacted Cyclohexane From the stockroom: 250-ml heating mantle and 50-ml RBF Pipette the dried solution into a 50-ml RBF, add 2 boiling chips and set-up for simple distillation using a heating mantle and variac as the heat source. Again have instructor check your set-up before turning on power. Start voltage setting at 45 and collect two distillation fractions in separate, previously weighed 125-ml E. flasks. Increase voltage as need arises. Set receiving flasks in an ice/water bath to help reduce the volatility of the distillate. Fraction #1 should be collected up to and around 850C. Once the temperature begins to rise quickly and/or significantly above 850C, switch receiving flasks. Obtain the mass and measure the refractive index for both fractions. Calculate the percent yield for the reaction and submit the fraction containing the chlorocyclohexane in a properly labeled bottle to instructor. Pour the other fraction into the hydrocarbon waste bottle located in the hood. Your instructor may wish a sample for GC analysis as well.