Organic chemistry Laboratory CH 200L (2012 2013) 2B-Ph Group 7 Experiment 8

Classification Tests for Organic Halides

Lesli Linka Mel L. Olivete, Feliz Jem V. Ong, Ralph Timothy S. Ong*, Aira Marie A. Ortega, Erikka Marie S. Pagkalinawan and Ramoncito Gabriel O. Paragas Department of Pharmacy, Faculty of Pharmacy University of Santo Tomas, Espana Street, Manila 1008

Date Submitted: September 4, 2012

Abstract
Organic halides are organic compounds containing a halogen atom bonded to a carbon atom. Most organic halides are synthetic and not flammable. To attain the goals of this experiment, different samples of organic halides: primary, secondary, and tertiary were classified according to their SN reactivity. Sample compounds of this experiment were analyzed with Beilstein test, alcoholic AgNO3, NaI with acetone. All the sample had produced a positive result with Beilstein test, affirming the presence of chloride ion. When all the sample compounds were reacted with 2% alcoholic AgNO3 to affirm SN1 reactivity or unimolecular phase. All the samples have exhibited the presence of white precipitate in different time except for chlorobenzene which exhibited a no reaction. Lastly, the compounds were reacted with NaI in acetone that exhibited a SN2 or bimolecular phase. It was observed that all the sample exhibited a white precipitate. The time required for each sample compound was different from that of SN1 phase. Therefore, the inference is that there are differences of the results attained from each S N mechanisms; furthermore, these differences attained can be used to classify organic halides.

Introduction

The objectives of this experiment were to differentiate primary, secondary, and tertiary organic halides based on SN reactivity and differentiate SN1 and SN2 mechanisms with organic halides. Sample compounds of chlorobenzene, n-butyl chloride, sec-butyl chloride, tertbutyl chloride were analyzed with Beilstein test, alcoholic AgNO3 and NaI in acetone. All samples produced a positive result with Beilstein Test. When the samples are reacted with AgNO3, tert-butyl chloride, sec-butyl chloride, nbutyl chloride produced a white precipitate in the said sequence and there is no reaction with chlorobenzene. In the test with SN2 reactivity all produced positive results with a white precipitate, n-butyl chloride first, followed by sec-butyl chloride then tertbutyl chloride and chlorobenzene. Organic halides are organic compounds in which one or more hydrogen atoms have been substituted by a halogen atom. The halogen atom can either be Chlorine, Fluorine, Bromine, or Iodine. Organic halides are considered as flame retardant and synthetic. If the alpha carbon atom is sp3 hybridized in the compound, the organic halide can be classified as primary, secondary or tertiary that is dependent on the degree of substitution of alpha hydrogen atom by an R group. Organic halides are can be classified depending on the halogen atom position

on the chain of carbon atoms. 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.

n-butyl chloride chloride

sec-butyl

tertbutyl chlorobenzene

chloride

By the use of substitution reaction with a nucleophile, the reaction of an electron pair donor (the nucleophile) with an electron pair (the electrophile). A sp3-hybridized electrophile must have a leaving group (X) in order for the reaction to take place (4). The reaction is SN1 or unimolecular if the rate of reaction is dependent on the organic halide and it is SN1 if the rate of reaction is dependent on both the

organic halide and the nucleophile. The following tests were performed: Beilstein test is a simple chemical test used in chemistry as a qualitative test for halides. It was developed by Friedrich Konrad Beilstein. To test for SN1 reactivity the samples were reacted with alcoholic AgNO3 and to test for SN2 reactivity it is reacted with NaI in acetone. In this experiment, the group should be able to attain the following objectives: (1) differentiate primary, secondary, and tertiary organic halides based on SN reactivity and (2) differentiate SN1 and SN2 mechanisms with organic halides. Methodology A. Beilstein Test : Copper Halide Test Procedure. A small loop was made with one end of the copper wire and heated on a nonluminous flame until the green color disappears. It was cooled then dip into the sample. A bluegreen or green colored flame indicates the presence of chlorine, bromine, or iodine.

precipitate forms and color were recorded.

Results Results obtained from experiment were tabulated (see table 1) Table 1. Reactions of Samples in Beilstein Test Sample Color of Flame n-butyl chloride Blue-green flame Sec-butyl Blue- green chloride flame Tertbutyl Blue-green chloride flame Chlorobenzene Green flame Table 2. Reactions of Samples with alcoholic AgNO3 Sample Color of Order of Precipitat appearance e of precipitate n-butyl White 3 chloride precipitat (3 minutes) e sec-butyl White 2 chloride precipitat (2 minutes) e tertbutyl White 1 chloride Precipitat (1 second) e chlorobenzen No 4 e reaction (striations appeared during first drop) Table 3. Reactions of Samples with NaI in anhydrous acetone Sample Color of Order of Precipitat appearanc e e of ppt. n-butyl White 1 chloride Precipitat (3 e seconds) Sec-butyl White 2 chloride Precipitat (6 e seconds) Tertbutyl White 3 chloride Precipitat (14 e seconds) Chlorobenzen White 4 e Precipitat (20 e seconds)

Green flame Copper Wire

B. SN1 Reactivity: Reaction with Alcoholic AgNO3 Procedure: 5 drops of the sample were added to 20 drops of 2% ethanolic AgNO3. The mixture was shaken and the time before the precipitate forms and color were recorded. C. SN2 Reactivity: Reaction with NaI in Acetone Procedure: 5 drops of the sample were added to 2 drops of 15% NaI in anhydrous acetone. It was mixed and the time before the

Discussion In the experiment, we were given samples of n-butyl chloride, sec-butyl chloride, tert- butyl chloride and we did classification tests for these organic halides. The first test was the Beilstein Test. This is a test for the presence of halide by the presence of a blue-green colored flame. All samples produced a green or blue green colored flame, indicating that all samples contain halides but this test is not enough to differentiate between Cl, Br and I. The blue-green color is due to the emission of light from excited states of copper halide that has vaporized in the burner flame. The CuX2 imparts the blue- green flame. Reactions involved: Cu + O2 RX + CuO CuO (black solid) CuX2+ CO2+H2O

reaction to occur because it parallels basicity. The solvent should be a polar, aprotic solvent. In terms of stereochemistry, It involves Walden inversion of configuration. The reaction occurs as the entering nucleophile attacks the halide 180 away from the leaving group. The reaction exhibits second-order kinetics and it is affected by steric effect caused by the bulky group of the reagents. The SN2 reaction favors primary and secondary substrates compared to SN1 reaction that favors tertiary substrates.

In the test for SN1 Reactivity by reaction with alcoholic AgNO3 tert-butyl chloride was the first to produce a white precipitate followed by sec-butyl chloride, n-butyl chloride and no reaction with chlorobenzene. The kinetics of the reaction is dependent on the alkyl halide. The more stable the carbocation intermediate the faster the rate of SN1 reaction. A good leaving group (halide) is important for the reaction to occur. 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. It involves inversion and retention. The SN1 reaction happens when substrate dissociate to a carbocation in a slow rate-limiting step, followed by a rapid attack of a nucleophile. This reaction shows first order kinetics and take place with racemization of configuration at the carbon atom. In the test for SN2 reactivity by reaction of NaI in acetone, n-butyl chloride is the first to show a white precipitate followed by sec-butyl chloride, tert- butyl chloride and chlorobenzene. The kinetics of this reaction is dependent on th alkyl halide and nucleophile. Due to steric effect, the substrate effect in SN1 reaction is the opposite in SN2 reactions. It favors primary and secondary substrates. A strong nucleophile is needed for

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