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CLASSIFICATION TESTS FOR ORGANIC HALIDES Maria Janine B. Abarientos, Kuia B. Allarde, Aliana Keshia P.

Andino Mary Viadelle E. Andrada and Nina Marian Robelea G. Ang Group 1 2C Pharmacy Organic Chemistry Laboratory
ABSTRACT This experiment was done in order to differentiate primary, secondary and tertiary organic halides based on their nucleophiic substitution reactivity and to differentiate SN2 and SN1 mechanisms of organic halides. The samples employed were n-butyl chloride, sec-butyl chloride, tert-butyl chloride and chlorobenzene, which were analyzed first with the Beilstein Test, a copper halide test, which indicates the presence or formation of a copper halide through the formation of a green flame. The next procedure was for the SN1 Reactivity, the compounds were reacted with alcoholic AgNO3 and were agitated until a precipitate was formed. Finally, for the SN2 Reactivity, the samples were reacted with NaI in Acetone in dry test tube. And was shaken and noted for a precipitate formed. In the Beilstein test, all produced blue-green flames indicating the presence of chlorine, bromine or iodine. In SN1 reactivity, 2 of the compounds formed white precipitate namely sec-butyl chloride and tert-butyl chloride, while the remaining samples had no reaction. But between these two compounds tert-butyl chloride reacts faster which only indicates that it is the most reactive in reaction with 2% ethanolic AgNO3 or SN1 reactivity. While in the SN2 reactivity n-butyl chloride is the fastest to react which only means that it is the most reactive among other compounds. For the chlorobenzene, however it yielded no reaction.

INTRODUCTION
Organic Halides (Organohalides or Alkyl Halides) are organic compounds in which one or more hydrogen atoms are substituted by a halogen atom namely fluorine, chlorine, bromine, and iodine. Unlike other organic compounds, most organic halides are synthetic. If the alpha carbon atom is tetragonal or sp3 hybridized in the compound, the organic halide may be classified as primary, secondary, or tertiary, depending on the degree of substitution of the alpha-hydrogen atom by an R group (1). The carbon which is attached with the halogen atom is linked up with only one other alkyl group in primary halogenoalkanes, whereas directly linked up with two and three other alkyl groups in secondary halogenoalkanes and tertiary halogenoalkanes respectively (2).

Figure 3. chloride

Chemical

structure

of

sec-butyl-

Figure 4. Chemical structure of chlorobenzene The Beilstein Test is a simple chemical test used as a qualitative test for halides. It was developed by Friedrich Konrad Beilstein. A positive test is indicated by a green flame caused by the formation of a copper halide. The test does not detect fluorine/fluorides (3). Treatment of an alkyl halide with a nucleophile/base results either in substitution or elimination. Nucleophilic substitution reactions occur by two mechanisms: SN1 and SN2. In the SN2 reaction, the entering nucleophile attacks the substrate from a direction 180 away from the leaving group, resulting in an umbrella-like inversion of configuration at the carbon atom. SN2 reactions are strongly inhibited by increasing steric bulk of the reagents and are favored only for primary substrates and simple secondary substrates. In the SN1 reaction, the substrate

Figure 1. Chemical structure of n-butyl-chloride

Figure 2. chloride

Chemical

structure

of

tert-butyl-

spontaneously dissociates to a carbocation, which reacts with a nucleophile in a second step. As a consequence, SN1 reactions take place with racemization of configuration at the carbon atom and are favored only for tertiary substrates (4). Also, if the rate of the reaction is dependent on the organic halide, the reaction is unimolecular: SN1. If the rate of reaction is dependent on both the organic halide and the nucleophile, the reaction is bimolecular: SN2 (1). The following tests were performed during the experiment: The Beilstein Test; Test for SN1 reactivity by reaction with 2%ethanolic AgNO3; Test for SN2 reactivity by reaction with 15% NaI in anhydrous acetone. This experiment aims to make the students capable of differentiating primary, secondary, and tertiary organic halides based on their SN reactivity. And be able to differentiate between SN1 and SN2 mechanisms with organic halides.

2. SN1 Reactivity: Alcoholic AgNO3

Reaction

with

5 drops of the sample were added to 20 drops of 2% ethanolic AgNO3. The mixture was shaken and the time the precipitate formed was recorded. It was also noted that the solutions of the reagents used was not turbid.

3. SN2 Reactivity: Reaction with NaI in Acetone


5 drops of the sample were added to 2 drops of 15% NaI in anhydrous acetone. The contents were mixed and the time that the precipitate formed was noted and recorded. Dry test tubes were used in this experiment to avoid contamination of the sample used.

RESULTS AND DISCUSSION


In the experiment, the researchers were tasked to do the Classification Tests for Organic Halides given different compounds such as n-butyl chloride, sec-butyl chloride, tertbutyl chloride and chlorobenzene. The results obtained from the experiment were tabulated as follows: Table 1. Reactions with Beilstein Tests
Sample n-butyl chloride Sec-butyl chloride Tert- butyl chloride Chlorobenzene Color of Flame Blue-green flame Blue- green flame Blue-green flame Blue-green flame

EXPERIMENTAL A. Sample Used


Sample Used: n-butyl chloride sec-butyl chloride tert-butyl chloride chlorobenzene

B. Procedure 1. Beilstein Test: Copper Halide Test


A small loop with one end of the copper wire was made. The loop was directly heated in the oxidizing zone of a non-luminous flame. It was a continuously heated until the green color imparted to the flame disappears. Then the loop was cooled and it was dipped into the sample and was again heated in a non-luminous flame. A blue-green (or green)-colored flame indicates the presence of chlorine, bromine, or iodine.

The first test was the Beilstein Test, which is a test for presence of halide through the presence of a blue-green flame. All of the samples produced blue-green flame indicating that all of the samples contain halides but still is not enough to differentiate chlorine from bromine or iodine. The blue-green flame that is produced is due to the emission of light from the excited state of copper halide that was vaporized in the burner flame. The CuX2 imparts the colored flame. The reactions involved are: Cu + O2 RX + CuO CuO (black solid) CuX2+ CO2+H2O

Figure 5. Beilstein Test: Copper Halide Test

Table 2. Reaction with 2% ethanolic AgNO3


Sample n-butyl chloride sec-butyl chloride tert- butyl chloride chlorobenzene Color of Precipitate No reaction White precipitate White Precipitate No reaction Order of appearance of precipitate -2 seconds 1 second No reaction

The table shows the results obtained for the SN2 reactivity by the reaction with 15% NaI in anhydrous acetone. It shows that n-butyl chloride is the first to precipitate followed by the sec-butyl chloride and the tert-butyl chloride which is the last to form a precipitate but with no reaction again with chlorobenzene. The kinetics of this reaction is dependent on th alkyl halide and nucleophile. The substrate effect indicates that the more stable the carbocation intermediate, the faster the SN1 reaction. -CH3 > 10 > 20 > 30 (due to steric effect) A good leaving group is also needed for a good reaction. TosO- > I- > Br- > Cl- > F- > HO-, H2N-, ROMore reactive less reactive A strong nucleophile is needed for reaction to occur because it parallels basicity. The solvent should be a polar, aprotic solvent. The reaction exhibits second-order kinetics and it is affected by steric effect caused by the bulky group of the reagents. The SN 2 reaction favors primary and secondary substrates compared to S N 1 reaction that favors tertiary substrates.

The table shows the results for the test for the SN1 reactivity. Tert-butyl chloride was the first to precipitate than sec-butyl chloride but does not react with neither n-butyl chloride nor chlorobenzene. The kinetics of the reaction is dependent on the alkyl halide. The substrate effect emphasizes that the more stable the carbocation intermediate, the faster the S N1 reaction. 30 > 20 > 10 > -CH3 ; reaction rate = k [RX] The nucleophile in an SN1 reaction is hardly affected. It does not enter into the reaction until after the rate-limiting dissociation has occurred; thus cannot affect the reaction rate. A good leaving group is needed in a reaction: TosO- > I- > Br- > Cl- > H2O More reactive less reactive The solvent used should be a protic, polar solvent that stabilizes the carbocation intermediate by solvation that increases the reaction rate. In terms of stereochemistry, this involves inversion and retention. Table 3. Reaction with 15% NaI in anhydrous acetone
Color of Precipitate White precipitate Light yellow precipitate Yellow Precipitate No reaction Order of appearance of precipitate 1 second 2 seconds 5 seconds No reaction

REFERENCES
[1]Bayquen A. et.al.(2009).Laboratory Manual in

Organic Chemistry.Quezon City: C&E Publishing Inc.do.edu/hndbksupport/ochemlabtech.html 2003 [2]http://chemicalland21.com/industrialchem/organic/


n-BUTYL%20CHLORIDE.htm September 11, 2011

[3]http://en.wikipedia.org/wiki/Beilstein_test September 10,2011 [4]Mcmurry J.(2010).Foundations of Organic Chemistry.Ortigas Avenue,Pasig City: Cengage Learning Asia Pte Ltd

Sample n-butyl chloride sec-butyl chloride tert- butyl chloride chlorobenzene