University of Santo Tomas Faculty of Pharmacy Organic Chemistry Laboratory

Alejandro, S.F; *Ang, K.C; Bautista, M.R; Bisa, H.H; Buena, P.L; Buiza, A.M.

Abstract Organic halides are organic compounds in which one or more hydrogen atoms have been substituted by a halogen atom. Most organic halides are synthetic and flammable. The main objective of this experiment is to differentiate primary, secondary, and tertiary organic halides based on their S N activity and make a distinction between S N1 and SN2 mechanisms with organic halides. Sample compounds of chlorobenzene, n-butyl chloride, sec-butyl chloride, tert-butyl chloride were analyzed with Beilstein test, alcoholic AgNO3 and NaI in acetone. All the sample compounds had produced a positive result with Beilstein test, affirming the presence of Chloride ion. When the compounds were reacted with 2% ethanoic AgNO to observe SN1 Reactivity, all has attained a white precipitate indifferent time required except for chlorobenzene which had observed to exhibit no reaction. While in the SN2 phase reactivity using NaI in Acetone, it was observed that all have exhibit the presence of white precipitate except for chlorobenzene; noted that the time required for each compound was different from that of S N1. It was observed that there are differences of the results attained from each SN reactivity or mechanisms and that these differences can be used to classify organic halides ________________________________________________________________________________________

Introduction Organic halides are organic compounds containing a halogen atom bonded to a carbon atom. The said halogen atom can either be chlorine, fluorine, bromine, or iodine. A halogen that have been substituted in one or more hydrogen atoms are organic compounds commonly known as organic halides. These compounds are considered to be flame retardant and synthetic. [1] The carbon attached to the halogen atom in organic halide is also known as the alpha () carbon. The -carbon can be classified as primary, secondary, or tertiary provided that it is an sp3 hybridized atom. It can be considered as primary when alkyl group is attached to an -carbon, secondary when two groups are attached to a -carbon, and tertiary when three groups attached to a carbon (Figure 1). The IUPAC name for halides is the same as branched chain hydrocarbons. The branch is named by shortening the halogen name to fluoro-, chloro-, bromo-, or iodo-. The halides can also be named by naming the group and using the names fluoride, chloride, bromide or iodide.

Figure 1: Types of Halogenoalkane

Organic halides reactivity depends on the halogen atom that is bonded to the carbon atom in the particular compound and 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 halogen alkanes, whereas directly linked up with two and three other alkyl groups in secondary halogen alkanes and tertiary halogen alkanes respectively. [2] The reactivity of alkyl halides is dominated by the attack of nucleophiles at the carbon atom that bears the halogen atom. This results in a nucleophilic substitution reaction. There is a wide range of nucleophiles that may be employed. Simple aryl halides do not tend to undergo

nucleophilic substitution as the attacking nucleophile is repelled by the high electron density of the aromatic ring. [3] The reaction mechanism is shown in Figure 1.2.

re-heated in the Bunsen burner. Green flame indicates the presence of halogen. [4] The experiment must be able to attain the following objectives: (1) to differentiate primary, secondary, and tertiary organic halides based on their SN reactivity, and tertiary organic halides based on their SN reactivity. (2) to differentiate SN1 and SN2 mechanisms with organic halides. Methodology: Experimental A. Samples used n-butyl chloride sec-butyl chloride tert-butyl chloride chlorobenzene 2% ethanoic AgNO3 15% NaI in anhydrous acetone B. Procedure Beilstein test was first performed. First, a loop was made on one end of the copper wire and pre-heated in the oxidizing zone of a nonluminous flame using a Bunsen burner. Then, each wire was then dipped into a sample again heated it in the non-luminous flame. In a positive result, the wire would emit a blue-green or green flame that would indicate the presence of a halogen. The next test was the SN1 reactivity test. AgNO3 was used in this test. Twenty drops of 2% ethanoic silver nitrate (AgNO3) were put on four test tubes. Five drops of each sample was then placed on their respective test tubes. The test tubes were shaken and recorded the time until a silver halide precipitate is formed. The color of the precipitate was noted by the group. The last test performed was the SN2 reactivity test. Twenty drops of 5% sodium iodide (NaI) in anhydrous acetone solution was placed in a test tube. Five drops of a

Figure 1.2: Nucleophilic Substitution

The mechanism of nucleophilic substitution for primary and secondary alkyl halides is abbreviated to SN2, short for Substitution, Nucleophilic, second order. It is a bimolecular reaction. [3] (Figure 1.3)

Figure 1.3: SN2 Reaction

As the number of substituents around the carbon center undergoing reaction increases, the substituents block the approach of the incoming nucleophile and consequently an SN2 mechanism becomes less favorable. [3] (Figure 1.4)

Figure 1.4: SN2 Reaction towards Secondary Alkyl Halides

In the case of a tertiary alkyl halide, loss of the halide occurs first to give a carbocation which then reacts with the nucleophile. This is called a SN1 reaction (Substitution, Nucleophilic, first order). [3] (Figure 1.5)

Figure 1.5: SN1 Reaction towards Tertiary Alkyl Halides

Beilstein test is a chemical test used as a qualitative test for halides (chlorine, bromine, or iodine). Test substance is added to the piece of pre-heated copper wire and

sample reagent was then added. The test tube was shaken until a precipitate was formed. The time it took for the precipitate to form and the color of the precipitate was also recorded. The procedure is then repeated using the rest of the sample reagents. Results and Discussion: After performing the experiment, results were obtain and recorded. In the Beilstein test, all of the samples that were set on fire emitted a green flame. Green flame indicates formation of a copper halide which shows the presence of a halogen. (Table 1, Figure 2) The concept behind this reaction is the following: Cu + O2 => CuO (black solid) RX + CuO => CuX2 + CO2 + H2O CuX2 is volatile and imparts a blue-green flame. Compound used n-butyl chloride sec-butyl chloride tert-butyl chloride chlorobenzene
Table 1: Beilstein Test Result

Beilstein Test green flame green flame green flame green flame

n-butyl chloride

sec-butyl chloride tert-butyl chloride

chlorobenzene

Figure 2 : Beilstein Test Result

For SN1 reactivity test, 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 reactions is dependent on the alkyl halide. The more stable the carbocation intermediate the faster rate of SN1 reaction. A good leaving group was important for the reaction to occur. The solvent used should be a protic, polar solvent that stabilizes the stereochemistry, this 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 takes place with racemization of configuration at the carbon atom. The results are shown in Table 2 and Figure 3. Compound used n-butyl chloride sec-butyl chloride tert-butyl chloride chlorobenzene
Table 2: SN1 Reaction Result

Reaction with 2% ethanolic AgNO3 2 mins. 10 sec. 5 sec. No reaction

Figure 2: SN1 Reaction Result

The last test performed was the SN2 reactivity test 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 no reaction for chlorobenzene. The kinetics of this reaction was dependent on the alkyl halide and nucleophile. Due to steric effect, the substrate effect in SN1 reaction was the opposite in SN2 reactions. It favors primary and secondary substrates. A strong nucleophile was needed for 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 degrees away from the leaving group. The reaction exhibits second-order kinetics and it was 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. (Table 3) Compound used n-butyl chloride sec-butyl chloride tert-butyl chloride chlorobenzene
Table 3: SN 2 R e a c t iv it y Te s t

Reaction with 15% NaI in anhydrous acetone 2 sec 4 sec 3 sec No reaction

References 1) Bayquen,A.,Cruz,C.,etal (2009). Laboratory Manual in Organic Chemistry.Quezon City, Philippines:C&E Publishing, Inc. 2) Organic Chemistry Portal. Nucleophilic Substitution. 3) Organic Halogen Compounds. Retrieved on September 15, 2013 from http://sydney.edu.au/science/chemistry/~george/halides.html 4) Science Dictionary. The Worlds Largest Online Science Dictionary. Retrieved on September 16, 2013 from http://thesciencedictionary.org/beilstein-test/