CLASSIFICATION TESTS FOR ORGANIC HALLIDES Chloe P. Valena, Jose Maria Q. Veloso, Norjem R. Villanueva, Jaquelyn C.

Wodi Group 10 2A Medical Technology Organic Chemistry Laboratory ABSTRACT

Organic halides are organic compounds in which one or more hydrogen atoms have been substituted by a halogen atom. The experiment was done for the purpose of differentiating the primary, secondary, tertiary organic halides based on their SN reactivity and also differentiates SN1 from SN2 mechanism with organic halides. Most organic halides are synthetic and not flammable. Qualitative tests for alkyl halides are useful in deciding whether the compound in question is a primary, secondary, or tertiary halide. The classification of organic halides was done through the use of Belstein test, the reaction of the organic halides with ethanolic silver nitrate, and the reaction with sodium iodide in acetone. Belstein test was used to check for halogens, but this did not differentiate the different halides. This test resulted in a blue-green flame for all of the compounds. The reaction test with 2% ethanolic silver nitrate was used to test for SN1 reactivity that shows a white precipitate. According to the test, tert-butyl chloride has the most SN1 reactivity followed by sec-butyl chloride and n-butyl chloride. To test for SN2 reactivity, a reaction test with 15% NaI in anhydrous acetone was conducted. According to the results, the compound with the most SN2 reactivity was n-butyl chloride, followed by, sec-butyl chloride and tert-butyl chloride. Chlorobenze is not SN1 and SN2 reactive because typical SN1 and SN2 mechanisms are not feasible in aromatic systems.

INTRODUCTION
An organic halide is a compound that contains one or more halogen atoms as part of its molecular structure. The halogen atom can either be Chlorine, Bromine, Fluorine, and iodine. The reactivity of organic halides depends on the halogen atom that is bonded to the carbon atom in the particular compound. Organoiodides are the most reactive and can be converted into many other compounds. Organobromides are less reactive than organoiodides but more reactive than organochlorides. Organofluorides are the least reactive of the organic halides. In carbon-halogen bond, halogens have significantly greater electronegativities than carbon except iodine. In result, this functional group is polarized so that the carbon is electrophilic and the halogen is nucleophilic. Organic halides are classified according to the position on the chain of carbon atoms. If the carbon, which is

attached to the halogen atom, is linked up to only one alkyl then it is considered as a primary alkyl halide. If the alpha carbon (the carbon attached to the halogen atom), is linked to two alkyl groups then it is classified as secondary. A tertiary alkyl halide is composed of an alpha carbon attached to three alkyl groups. Figure 1 shows the different organic alkyl halides classifies as primary, secondary, and tertiary.

Figure 1. Structures of Butyl Chloride and Chlorobenzene

The term SN2 means that two molecules are involved in the actual transition state as shown in figure 2.

Figure 2. Bimolecular Nucleophilic Substitution. The departure of the leaving group occurs simultaneously with the backside attack by the nucleophile. The SN2 reaction thus leads to a predictable configuration of the stereocenter - it proceeds with inversion. As shown in figure 3, the SN1 reaction, a planar carbenium ion is formed first, which then reacts further with the nucleophile. Since the nucleophile is free to attack from either side, this reaction is associated with racemization.

small loop was made at one end of the wire. Then, the loop was heated directly in the oxidizing zone of a non-luminous flame. The loop was allowed to cool slightly then dipped into the liquid sample. For the first flame test, the loop was heated in the inner zone and then the outer zone near the edge of the flame. SN1 Reactivity with Alcoholic AgNO3: To start off, the solution should not be turbid when used. Five drops of the sample was added to 20 drops of 2% ethanolic AgNO3. The solution was then shaken and the time it took for the solution to precipitate was recorded. SN2 Reactivity reaction with NaI in Acetone: Five drops of the sample was added to 2 drops of 15% NaI in anhydrous acetone. The contents were mixed and the time it took for a precipitate to form was recorded.

RESULTS AND DISCUSSION

Figure 3. Unimolecular Nucleophilic Substitution In both reactions, the nucleophile competes with the leaving group. Because of this, one must realize what properties a leaving group should have, and what constitutes a good nucleophile. For this reason, it is worthwhile to know which factors will determine whether a reaction follows an SN1 or SN2 pathway. The objective of the experiment was to determine which organic alkyl halide was the most SN1 and SN2 reactivity by differentiating the reactivity of primary, secondary, and tertiary compounds. In this experiment, we were given samples of n-butyl chloride, secbutyl chloride, tert-butyl chloride, and chlorobenzene. The results of the experiment are tabulated in Table 1. The first test that was done was the Beilstein test which indicates the presence of a halide. The presence of a halide was determined by the presence of a blue-green flame. Figure 4 shows the process of the beilstein test.

EXPERIMENTAL
A. Compounds used: n-butyl chloride, sec-butyl chloride, tert-butyl chloride, and chlorobenzene. B. Procedure Beilstein Test: Copper Halide Test A copper wire was obtained and a

Figure 4. Beilstein Test All of the samples produced a bluegreen flame indicating that all compounds contain a halide. This test however, is not able to

differentiate between the different halides. The test is based on the reaction of chlorine with copper compounds at the high temperatures found in burner flames. These conditions produce excited, greencoloured copper atoms or ions that cause the blue-green flame. In the test for SN1 Reactivity by reaction with 2% ethanolic AgNO3, tert-butyl chloride was the fastest to react. The white precipitate formed around 25 seconds after tert-butyl chloride was mixed with 2% ethanolic AgNO3. The second compound that formed a precipitate was sec-butyl chloride, followed by n-butyl chloride at around three minutes as shown in Figure 5.

Figure 5. SN1 Reactivity Formation of White Precipitate With tert-butyl chloride having the most reactivity with 2% ethanolic AgNO3, this indicates that tert-butyl chloride has the most SN1 reactivity. An SN1 reaction occurs by spontaneous loss of the leaving group before the incoming nucleophile approaches. Loss of theleaving group gives a carbocation intermediate, which then reacts with the nucleophile in a second step to yield the substituent product. This two step process explains why tertiary halides react rapidly with 2% ethanolic AgNO3. SN1 reactions can occur only when the stable carbocation intermediates are formed. The positively charged carbon can therefore react with a nucleophile equalye from either side. Chlorobenzene did not form a precipitate indicating that SN1

reactivity is not feasible in aromatic compounds. The test for SN2 Reactivity by reaction NaI in anhydrous acetone, the results turned out to be that nbutyl chloride was the fastest to react with the solution. The second fastest was sec-butyl chloride followed by tert-butyl chloride. Although all of the compounds reacted almost immediately after it was mixed with the NaI in anhydrous acetone, n-butyl chloride still has the most SN2 reactivity. The reactions that occur are SN2 substitutions in which iodide ion is the nucleophile; the order of reactivity is primary > secondary > tertiary. Due to steric effect, the substrate reaction in SN1reaction is the opposite in a SN2 reaction. SN2 reactions take place in a single step without intermediates when the entering nucleophile approaches the substrate from a direction 180 degrees away from the leaving group. The nucleophile forces out the leaving group. The ease with which a nucleophile can approach a substrate to carry out an SN2 reaction depends on steric accessibility to the halide-bearing carbon. Bulky substrates, in which the halide-bearing carbon atom is difficult to approach, react much more slowly than those in which the carbon is more accessible.

REFERENCES
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