CLASSIFICATION TESTS FOR ORGANIC HALIDES

Gerone Ann Tolentino, Sofia Blanca Trinidad, Ma. Jessa Victoria Vallangca, Kristine Nicole Villanueva, Nicole Anne Yanquiling Group 8 2G-Pharmacy Organic Chemistry

ABSTRACT
Organic halides are organic compounds that contain a halogen attached to a carbon atom. They usually react through SN1 or SN2, depending on the strength of the nucleophile. Most organic halides are synthetic and non-flammable. Furthermore, they are classified as to either primary, secondary, or tertiary. In this experiment, the primary, secondary, and tertiary organic halides were subjected to tests to know which reacts through SN1 or SN2 mechanisms and which reacts faster toward it. N-butyl chloride, sec-butyl chloride, tert-butyl chloride and chlorobenzene were analyzed through Beilstein test, Alcoholic AgNO3, and NaI in acetone. [1] All the sample compounds yielded a positive result with the Beilstein test, indicating the presence of chloride. When the sample compounds were made to react with 2% ethanolic AgNO3, all compounds produced a white precipitate except for chlorobenzene. Same results were obtained when they were all made to react with NaI in acetone, but had a different rate of producing the white precipitate as compared to that of 2% ethanolic AgNO3. Therefore, it can be concluded that the difference among organic halides lies in their reactivity towards the different SN mechanisms. _____________________________________________________________________________

INTRODUCTION
A halogen attached to a long chain of carbon atoms is referred to as an organic halide. They can be classified as primary, secondary, or tertiary, depending on whether the carbon containing the halogen is attached to 1 carbon, 2 carbons, or 3 carbons. These compounds react through nucleophilic substitution (SN), which is further subdivided into SN1 and SN2. [2] The difference between SN1 and SN2 lies in the rate-determining step. If the rate of reaction depends on the organic halide, SN1 reaction predominates and is said to be unimolecular. On the other hand, if the rate of reaction is dependent on both the organic halide and the nucleophile, SN2 reaction predominates and is said to be bimolecular. [1] A nucleophile is any reagent that gives off an unshared pair of electrons to form a new covalent bond. In nucleophilic substitution, halogens are usually the leaving group and substitution of the nucleophile takes place on an sp 3 hybridized atom carbon atom. The reaction for SN1 happens in two steps and takes place in a polar protic solvent and if the nucleophile has a poor strength. SN2 on the other hand happens in only one step and takes

place in a polar aprotic solvent and if the nucleophile is strong as needed for the back-side attack. [3] To know whether the sample compounds tested contained a halide, they were subjected to the Beilstein test. A green flame indicates the presence of a halide. To observe the reactivity of the compounds to SN1, they were made to react with alcoholic AgNO3; and to observe their reactivity to SN2, they were made to react with NaI in acetone. The objectives of the experiment is to (1) differentiate primary, secondary, and tertiary organic halides based on their SN reactivity and (2) differentiate SN1 and SN2 mechanisms with organic halides. [1]

EXPERIMENTAL
A. Samples used The samples used for this experiment are n-butyl chloride, sec-butyl chloride, tert-butyl chloride, chlorobenzene, 2% ethanolic AgNO3, and 15% NaI in anhydrous acetone. B. Procedure 1. Beilstein Test A small loop was made with one end of the copper wire. The loop was heated directly in the oxidizing zone of a non-luminous flame. The heating was continued until the green color imparted to the flame disappeared. The loop was slightly cooled and was dipped into each of the samples. The loop with the sample was again heated in a non-luminous flame: first in the inner zone, then in the outer zone near the edge of the flame. A blue-green or green-colored flame indicated the presence of chlorine, bromine, or iodine.

Fig. 1 Green-colored flame for Beilstein Test

2. SN1 Reactivity: Reaction with Alcoholic AgNO3 5 drops of the sample were added to 20 drops of 2% ethanolic AgNO3. The sample was shaked and the time in seconds or minutes for a silver halide precipitate to form was recorded. Fig. 2 Results for SN Reactivity Tests

3. SN2 Reactivity: Reaction with NaI in Acetone 5 drops of the sample were added to 20 drops of 15% NaI in anhydrous acetone. The contents were mixed and the time in seconds or minutes it took for the precipitate to form was recorded.

RESULTS AND DISCUSSION

The results obtained from the experiment are as follows: Table 1. Data obtained from Beilstein Test Compounds Used n-butyl chloride sec-butyl chloride tert-butyl chloride chlorobenzene

Beilstein Test Green flame Green flame Green flame Green flame

The Beilstein test was used to determine whether the compounds tested contained a halide. All the samples were subjected to heat in the oxidizing zone of a non-luminous flame and all showed a green-colored flame, which indicates the presence of a halide. This test is the simplest method in determining the presence of a halide in a compound. It does not, however, specify what halide is contained in the compound.

Table 2. Data obtained from SN1 Reactivity Test Compounds Used n-butyl chloride sec-butyl chloride tert-butyl chloride chlorobenzene

Reaction with 2% ethanolic AgNO3 White precipitate formed (11 secs.) White precipitate formed (8 secs.) White precipitate formed (3 secs.) No reaction

In this test, tert-butyl chloride formed the white precipitate the fastest. This is due to the stability of the carbocation intermediate of tert-butyl chloride. Thus, it is observed that the more stable the carbocation intermediate, the faster it reacts through S N1. In order for an SN1 reaction to occur, there must be a good leaving group and a polar protic solvent. With regards to stereochemistry, an SN1 reaction exhibits racemization. Moreover, an SN1 reaction is a twostep process, as the leaving group breaks away from the carbon it is attached to first followed by the attack of the nucleophile to the carbocation intermediate. Table 2. Data obtained from SN2 Reactivity Test Compounds Used n-butyl chloride sec-butyl chloride tert-butyl chloride chlorobenzene

Reaction with 2% ethanolic AgNO3 White precipitate formed (2 secs.) White precipitate formed (4 secs.) White precipitate formed (5 secs.) No reaction

In this test, n-butyl chloride was the fastest compound to from the white precipitate due to its lesser steric effect. It is then observed that SN2 reaction is the opposite of SN1 reaction. The lesser steric effect the alpha-carbon exhibits, the faster it reacts with SN2. In an SN2 reaction, there must be a strong nucleophile and a polar aprotic solvent. With regards to stereochemistry, an SN2 reaction exhibits inversion. Also, an SN2 reaction is a one-step process, wherein the nucleophile attacks the alpha-carbon from the opposite side of the leaving group, more known as the back-side attack.

SOURCES
1. University of Santo Tomas Faculty of Pharmacy Organic Chemistry Group. (2009). Laboratory Manual in Organic Chemistry. 893 EDSA, South Triangle, Quezon City: C&E Publishing, Inc.

2. Brown, W.H. and Poon, T. (2014). Introduction to Organic Chemistry (5th ed.). John Wiley & Sons, Inc., 111 River Street, Hoboken, New Jersey 3. McMurry, G., et al. Organic Halogen Compounds. Retrieved from

http://sydney.edu.au/science/chemistry/~george/halides.html