CLASSIFICATION TESTS FOR ORGANIC HALIDES Rey-Ann Valencia, James Dominic Vergara, John Mark Villena, Rikkamae

Zinca Marie Walde, Ron Lee Zamora, Kirk Matthew Zhu Group 10 2A Biochemistry Organic Chemistry Laboratory ABSTRACT
Samples of n-butyl chloride, sec-butyl chloride, tert-butyl chloride, and chlorobenzene were given to the group for analysis. They were analyzed using the Beilstein test, ethanolic AgNO3, and NaI in anhydrous acetone. All samples produced positive results in the Beilstein test. Upon testing the samples¶ reactions with AgNO3, tert-btyl chloride immediately gave a positive result which is a white precipitate. Sec-butyl chloride and chlorobenzene produced a turbid solution after testing with AgNO3 while n-butyl chloride gave a negative result. In the test for Sn2 reactions with NaI in anhydrous acetone, only n-butyl chloride gave a negative result while the rest of the samples exhibited a positive result which is also a white precipitate.

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. 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. Organic halides are not flammable and are mostly synthetic. The carbon attached to the halogen atom in an organic halide is known as the alpha ( ) carbon. The -carbon can be classified as either primary, secondary, or tertiary provided that it is an sp3 hybridized carbon. It is considered primary when an alkyl group is attached to the carbon, secondary when two alkyl groups are attached to the -carbon and tertiary if three alkyl groups are attached.

A tertiary organic halide, tert-butyl bromide.

Nucleophilic substitution is a reaction in which an incoming nucleophile replaces another group. Due to the electronegativity differences between carbon and the halide, the C-X bond is polar with a partial positive charge ( +) on the carbon atom and a partial negative charge ( -) on the halogen. Halogens are good leaving groups and can be replaced by a nucleophile. The reactivity of organic halides can be determined by its rate-determining step and the number of molecules used in the reaction. It can either be unimolecular (SN1) or bimolecular (SN2). The nucleophilic substitution reaction is unimolecular if the reaction rate is dependent on the organic halide. It is usually tertiary alkyl halides that react well in SN1 reactions. The reaction is bimolecular if the rate is dependent on the organic halide and the nucleophile. This is an example of a unimolecular nucleophilic substitution reaction: y The Rate Determining Step--Formation of the carbocation:

A primary organic halide, n-ethyl bromide.

General structural formula of a secondary organic halide.


Followed by attack of the nucleophile on the carbocation:

B. Apparatus and Equipment/Set-up Test tubes Matches Copper Wire Bunsen burner Pasteur pipettes C. Procedure exercise The group prepared and gathered all the needed materials and samples for the experiment. First, the group made a loop on copper wires and heated them in the oxidizing zone of a non-luminous flame using a Bunsen burner. Each wire was then dipped into a sample and again heated it in the non-luminous flame for the Beilstein test. In a positive result, the wire would emit a blue-green or green flame that would indicate the presence of a halogen. Next, the group performed the test for SN1 reactivity which makes use of AgNO3. Twenty (20) drops of 2% ethanolic silver nitrate (AgNO3) were put on four (4) test tubes. Five(5) drops of each sample was then placed on their respective test tubes. The group was then tasked to shake the test tubes and record the time until a silver halide precipitate is formed. The group was also tasked to note the color of the precipitate. For the test in SN2 reactivity, the group used twenty (20) drops of 5% sodium iodide (NaI) in anhydrous acetone solution and placed in on a test tube. Five (5) drops of a 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.

y The removal of a proton by the bromine:

An example of a substitution reaction:



The Beilstein test is a simple chemical test used in chemistry as a qualitative test for halides which was developed by Friedrich Konrad Beilstein. It was then widely used as a qualitative test for halides. A copper wire is cleaned and heated in a Bunsen burner flame to form a coating of copper(II) oxide. It is then dipped in the sample to be tested and once again heated in a flame. A positive test is indicated by a green flame caused by the formation of a copper halide. The reactions involved in this test are: Cu (s) + O2 (g) --> CuO (s) Adding the organic halide to the wire initiates this reaction upon heating: CuO + 2 R-X --> CuX2 + 2 R-O-X The volatile CuX2 reacts with the flame to produce another flame, which is bluish-green or green in color. In this experiment, the group should be able to differentiate primary, secondary, and tertiary organic halides based on their nucleophilic substitution reactivity and to differentiate SN1 and SN2 reactions in organic halides.

Sample used n-butyl chloride Sec-butyl chloride Tert-butyl chloride Chlorobenzene Table 1. Result in Beilstein test Green flame Blue-green flame Green flame Green flame

A. Samples used n-butyl chloride sec-butyl chloride tert-butyl chloride chlorobenzene 2% Ethanolic AgNO3 15% NaI in anhydrous acetone

Table 1 displays the results that the group acquired in the Beilstein test. As stated, only secbutyl chloride emitted a blue-green flame while the rest of the samples emitted only a green flame. All results in recorded in this procedure are considered positive since the Beilstein test is used to detect the presence of halides.

Sample used n-butyl chloride Sec-butyl chloride

Reaction with 2% AgNO3 No precipitate formed Turbid solution formed Immediate precipitation (white precipitate) Turbid solution formed

This table shows the results that the group collected while testing for SN2 reactivity of the samples given. Only n-butyl chloride gave a negative result forming no precipitate while the rest formed white precipitates. Theoretically, nbutyl chloride is supposed to react with the NaI solution since it is the most SN2 reactive of all the samples given. Chlorobenzene is not supposed to have a positive result for theoretically is not supposed to react in bimolecular nucleophilic substitution reactions.

y Bayquen, A.V., Cruz, C.T., de Guia, R.M., Lampa, F.F., Pena, G.T., Sarile, A.S., Torres, P.C. (2009). Laboratory Manual in Organic Chemistry. Quezon City: C & E Publishing, Inc. Nucleophilic Substitution of Alkyl Halides. philic%20Substitution%20of%20Alkyl%20 Halides.pdf SN1 Reaction. nces/chemistry/organicchemistry/Commo nReaction/Unimolecular/Unimolecular.htm

Tert-butyl chloride


Chlorobenzene Table 2.


The table above shows the results of the test for SN1 reactivity that the group has garnered. Only tert-butyl chloride produced a precipitate, which is AgCl. This result is positive. The other samples did not react well with AgNO3 thus producing only a turbid solution, or forming no precipitate at all. Both results are considered negative. Based on these results, the group noted that only tertiary organic halides are highly reactive during unimolecular nucleophilic substitution reactions.

Sample used

Reaction with 5% NaI in anhydrous acetone No precipitate formed Immediate precipitation (white precipitate) Immediate precipitation (white precipitate) Immediate precipitation (white precipitate)

n-butyl chloride

Sec-butyl chloride

Tert-butyl chloride

Chlorobenzene Table 3.

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