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The complete report of Organic Chemistry I with the title Preparation of Tertiary Butyl Chloride, which is made by: Name : Ria Natalia Dianty

Reg. Number : 101304152 Group/Class : I/ICP Chemistry

Have been check and consulted by assistant and assistant coordinator, so this report is accepted.

Makassar, June

2011

Assistant Coordinator

Assistant

Ahmad Fudhail, S.Pd.

Achmad Rante Suparman, S. Pd.

Known by, Responsibility Lecturer

Iwan Dini, S.Si., M.Si.

A. Title of Experiment The title of this experiment is Preparation of Tertiary Butyl Chloride.

B. The Aim of Experiment At the end of this experiment, students are expected to skilled about these following things: 1. The way to arrange and use the apparatus that needed in preparation of liquid organic compound, such as replux, solvent extraction, using the separation funnel, drying, filtration, and distillation. 2. The principles of aliphatic nucleophilic substitution. 3. The specific difference between SN1 and SN2

C. Preview of Literature Tert-butyl chloride is a colorless, liquid organic compound at room temperature. It is sparingly soluble in water, with a tendency to undergo spontaneously solvolysis when dissolved into it. The compound is flammable and volatile, and its main use as a starting molecle to carry out nucleophilic substitution reactio, to produce different substances, ranging from alcohols to alkoxide salt (Wikipedia. 2011). Tert-butyl chloride can be synthesized in the laboratory by SN1 reaction of tert-butyl alcohol with concentrated hydrocholric acid (Wikipedia. 2011). The hydroxile group in tert-butyl alcohol is the easiest group that can be susbtituted and this causes alcohol can react with concentrated HCl in room temperature. That reaction is necleophilic substituion reaction, SN1 type. That involve formatting of intermediate compound carbocation ion that relatively stable (Tim Dosen Kimia Organik. 2011). In organic chemistry, nucleophilic substitution us a fundamental class which an electron nucleophilic selective bonds with or attacks the positive or partially positive charge of an atom a group or atom called the leaving group; the

positive or partially positive atom is referred to as elctyrophile (Fessenden. 1987). Generally, nucleophilic substitution has reaction as:
Nu :
nucleophilie (netrall)

R:L
substrate

R : Nu+
product

: Lleaving group

or

Nu :
anion

R:L

R : Nu

: L-

This reaction can be explained by bond break concept and formning of a heterolitic bond. R L will undergo bond break heterolitically so that produced L that has fill orbital and R that has empty orbital. Then, this process is continued by the second process that is overlaping between empty orbital R and fill orbutal Nu:. These processes can be take place taken place consecutively or concurrently. L that is called as the leaving group in this mechanism is a nucleophilic that become product (Rasyid. 2009). In 1935, Edward D. Hugehes and Sir Christopher Ingold studied nucleophilic substutution reaction of alkyl halides and related compounds. They proposed that therewere two main mechanism at work, both of them competing with eah other. The two mechanism are the SN1 and SN2 reaction. S stand for chemical substitution, N stand for nucleophilic, and the number represens the kinetic order of the reaction (Merill. 1987). In the SN2 reaction, the addition of the nucleophilic and the elimination of leaving group take place simultaneously. SN2 occures where the central carbon atom is easily accessible to the nucleophile. Reaction of bromoethame with hydroxide ion that produce ethanol and bromide ion is example of SN2 reaction.

CH3 H C H Br

OH

HO

C H

CH3 Br

H C HO

CH3 H

Br

The mechanism show us that the breaking of bond and forming of bond taken place conccurrently (Fessenden. 1982) The first-order dependen the reaction rate on both X and R3CY concentration support the view of that the rate controlling step of the reaction involves the condition of X and R3CY. The fact that the attaching group, X, is always has an unshared pair elactrons is evidence for the nucleophilic character of the attack. Since, the displaced group, Y, also has an unshared pair of electrons, it seems reasonable that the reaction consists of a nucleophilic attack of Xon carbon, in which the unshared pair electron pair on X forms the new X C bond and displace Y with its electron pair (Hine. 1962). By contras SN2, the SN1 involves two steps. SN1 reaction tend to be important when the central atom carbon of the substrate is surrounded by butyl group, both because such groups interfere sterically with SN3 and because a highly substituted carbon forms a stable carbocation (Merill. 1987). Reaction of SN1 is ionic reaction. It mechanism is complex bacause of presence of solvent molecule, RX molecule, and transition ions that is formed. Reaction SN1 of a tert-halide alkyl is stepwise reaction. Firts step is breaking the halide alkyl to become ions, halide ion and carbocation ions. Because of this reaction involves ionization, these reaction are supported with polar solvent, like H2O that can stabilize the ions by solvat 1st step: (CH3)3C Br (CH3)3C+ ------ Br [(CH3)3C+] + Br

The second steps is melding of carbocation with nucleophilic (H2O) produce initial product, a protobated alcohol.

CH3 H3C C
+

CH3

CH3 OH H 3 H3C C CH3 OH

+

H2O

H3C

CH3

CH3

The last steps is releasing H+ from the protonated alchol in a acid-base reaction with the solvent.
CH3 H3C C CH3 OH
+

CH3

H2O

H3C

C CH3

OH

H3O

OH

(Fessenden. 1982). The mechanism reaction of tert-butyl choloride are: 1st step: The acid protonates the alcohol HCl
CH3 H3C C CH3 OH

H+ + ClCH3 H O
+

+H

H3C

C CH3

2nd step: Water leaves the protonated tert-butyl alcohol and forming carbocation
CH3 H3C C CH3 O H
+

tert-

H3C H3C C
+

H2O

CH3

3rd step: the chloride ion will attack the carbocation.

CH3 H3C C
+

CH3

Cl

H3C

C CH3

Cl

CH3

tert-butyl chloride

D. Apparatus and Chemicals 1. Apparatus a. Separation funnel 250 mL b. Funnel c. Volumetric glass d. Stirring rod e. Spray bottle f. Beaker g. Erlenmeyer 250 mL h. Stative and clamp i. Balance j. Dropped pipette

2. Chemicals a. Tertiary butyl alcohol b. Concentrated HCl c. Solution of NaHCO3 5% d. CaSO4 anhydrous e. Water/Aquadest f. Filter paper g. Tissue

E. Work Procedure 1. Filled separation fnnel with 16 mL of tertiary butyl alcohol and 42,5 mL concentrated HCl. 2. Shaked the mixture for 20 minutres. In every shaking, loose the separation funnel tap to reduce the pressure. 3. Stilled mixture for a while until the mixture separated becone two layers. 4. Took off the acid layer at the lower layer.

5. Washed halide with 10 mL NaHCO3 5%, then with 10 mL of water. 6. Dried the solution with CaSO4 anhydrous. 7. Filtered the liquid through a funnel that had been layered with fold filter paper. 8. Measured the volume of liquid.

F. Observation Result No. 1. 2. 3. 4. 5. 6. Treatment 16 ml (CH3)3COH + 42,5 mL HCl (concentrated) Shaked for 20 minutes Top layer + 10 mL NaHCO3 5% Top layer + 10 mL H2O Top layer + 3 gram CaSO4 anhydrous Filtered 2 layers
colorless colorless

Result
colorless

2 layers
colorless colorless

2 layers
colorless colorless

2 layers
colorless

colorless solution + white precipitate

Colorless solution (tert- butyl chloride 1,9 mL)

G. Data Analysis Known: (CH3)3COH (CH3)3CCl mass (CH3)3COH volume (CH3)3COH = 0,778 gr/mL = 0,84 gr/mL = 12,5 gram = = n (CH3)3COH v HCl Mr HCl = 0,17 mol = 42,5 mL = 36,5 gram/mol = 16 mL

mass of HCl

=v = 1,18 gram/mL 42,5 mL = 50,15 gram

n of HCl

= = (CH3)3COH + HCl 1,37 mol 0,17 mol 1,20 mol = 1,37 mol (CH3)3CCl 0,17 mol 0,17 mol + H2O 0,17 mol 0,17 mol

Initial : 0,17 mol React : 0,17 mol Final : 0

Mr (CH3)3CCl Mass of (CH3)3CCl teoritically

= 92,5 gram/mol = mol Mr = 0,17 mol 92,5 gram/mol = 15,72 gram

volume (CH3)3CCl

= 1,9 mL

mass of (CH3)3CCl in experiment= volume = 1,9 mL 0,84 gram/mL = 1,596 gram Yield (rendemen) = = = 10,15 %

H. Discussion In this experiment, the first step that was done is mixed 16 mL tert-butyl chloride with 42,5 mL concentrated HCl solution into a separation funnel. Then, the mixture was shaked for 20 minutes. In every shaking, the separation funnel tap must be loosened to reduce the pressure in separataion funnel. If not. The separation funnel can be break because of the pressure in separation funnel is to

high. Meanwhile, the function of shaking the mixture in separation funnel is to make the reaction between ter-butyl alcohol with HCl to produce tert-butyl chloride proceed easier. The reaction that take place during shaking is (CH3)3COH + HCl (CH3)3CCl + H2O

After shaking for 20 minutes, the misture was stilled until it separated to become two colorless layers. The acid layer is on the lower layer, while the halide layer is on the top layer. It is because of the density of tert-butyl chloride is smaller than the density of hydrochloric acid. The hydrochloric acid layer that excess was took off and removed. Then, the halide layer was washed with solution of NaHCO3 5%. The purpose is to remove the acid that excess in separation funnel. Then, the halide acid was washed again with water to take off the salt excess and all impuritied that contained in separation funnel.. in this process, the halide acid always on the top layer because its density is smaller than the other compounds. After washing, the halide layer was dried with CaSO4 anhydrous. The function of CaSO4 anhydrous is to bond the water that still mixed with halide layer, so that was got tert-butyl chloride. To separate between liquid tert-butyl chloride and CaSO4 hydrate was done filtering process by using funnel that layered with folded fiilter paper. From this process, was got tert-butyl chloride as much as 1,9 mL (1,596 grams) with yield (rendemen) is 10,15%. The yield is different with the mass hoped theory because the shaking was not done vigorously and the time was not enough so the tert-butyl alcohol and HCl not react completely. Beside that, during the loosened of separation funnel tap some of the mixture was gushed from separation funnel.

I. Closing 1. Conclusion Based on the experiment that had been done, can be concluded that: a. In preparation of tertiary butyl chloride the techniques that use aree separation by using separation funnel, filtration, and drying.

b. Aliphatic nucleophilic substitution reaction is substitution reaction of a functional group or molecule by a species that fill with electron and attack the molecule. c. SN1 reaction is reaction that involves a particle and take place in 2 steps. While, SN2 is reaction that involves 2 particles and take place in 1 step. d. The reaction that occurs i preparation of tert-butyl chloride is: (CH3)3COH + HCl (CH3)3CCl + H2O

with yield (rendemen) that got in experiment is 10,15%.

2. Suggestion For the next apperentice are expected to mastering all the work procedure of this experiment, so that the experiment can be done fluently. And they are expercted to shake the mixture as strong as possible, so that HCl and tert-butyl alcohol will react completely. The last but not least, they have to be carefull to work because the chemicals are hazard.

BIBLIOGRAPHY
Fessenden, Ralp J. 1982. Kimia Organik Jilid 1 Edisi Ketiga. Jakarta: Erlangga. Hine, Jack. 1962. Physical Organic Chemistry. Tokyo: Kogakusha Company. Merill. 1987. Chemistry a Modern Course. Sydney: Merill Publish Co. Rasyid, Muhaidah. 2009. Kimia Organik I. Makassar: Badan Penerbit UNM Tim Dosen Kimia Organik. 2011. Penuntun Praktikum Kimia Organik I. Makassar: Jurusan Kimia, FMIPA, UNM. Wikipedia. 2011. tert-Butyl Chloride. http://en.wikipedia.org./wiki/tert-

Butyl_Chloride, Accessed on May, 18th 2011.

ANSWER
1. n-Butyl alcohol and sec-butyl alcohol are example of primary and secondary alcohol. n-butyl alcohol and sec-butyl alcohol cannot be changed become is chloride by mix and shake it with concentrated HCl only. Is cause by primary and secondary alcohol is less reactif and need support by ZnCl2 or another catalyst. 2. HI is halide acid that strongest in nucleophilic substitution of alcohol. the series of the reactivity of halide acid is HF < HCl < HBr < HI. The increasing of the paower of acid and the increasing of the nucleophilic cause the increasing of reactivity againts ROH. 3. Alcohol will not undergo necleophilic substitution with base or neutrall solution because the OH group that becomes the leaving group from alcohol is same with the nucleophile species.