Preparation of asetanilide

HERMIN HARDYANTI UTAMI (111 304 0202)

CHEMISTRY DEPARTMENT MATHEMATIC AND SCIENCE FACULTY STATE UNIVERSITY OF MAKASSAR 2012

RATIFICATION PAGE The complete report of Organic Chemistry II with the title of “Preparation of Acetinilide” which made by : Name

: Hermin Hardyanti Utami

ID

: 111 304 0202

Group

: VII

Class

: ICP B

Have been checked by assistant and assistant coordinator. So, this report is accepted. Makkassar, December 2012 Assistant Coordinator

Assistant

Fandi Ahmad, S.Pd.

Burhanuddin, S.Pd

Known By, Responsibility Lecturer

Dra. Hj. Ramdani, M.Si.

A. Title of Experiment Preparation of Acetanilide B. Purpose of Experiment 1. Skilled to set and use equipment ansyntesis of organic substance 2. Explain the rise refining techniques 3. Explain principle of chemistry amine the derivative compound C. Backround Amine is organic compound that contain nitrogen atom trivalen that bond with one or two or three carbon atomic. If in structure formula, amina is derivate from ammonia that one, two, or three hydrogen atomic changed by alkil or aril group. Therefore, uf changer group hydrogen atomic in ammonia like aril group (R), then structure of aliphatic amine that maybe happen is RNH2, R2NH or R3N. if changer group us aril (Ar) will see same formula (Rasyid, 2009:187). Classification and namecleature of amina. Amina can grouped as primery, secondary, and tersiery, according subtituen of alkil or aril that bonded wuth nitrogent. 1C bond CH3NH2 Alkylamine primery

2C bond

3C bond

-NH-CH3

(CH3CH2)3N

arilalkilamine secondary

trialkilamine tertier

A nitrogen amine can have four group or atomic that bond in this way, nitrogen is the part of positive ionic. This compound devide two parts. If one or more that bond is H then this compound called amine salt. If forth the group is aril or alkyl (not H in N), then compound called cuartener Ammonium salt: Amine salt (CH3)2NH2+Cl Dimethyl ammonium chloride

N-methylpiperidium bromida

Salt from secondary amine

salt from tersier amine

Cuartener ammonium salt (CH3)4N+Cl

CH3CO2CH2CCH2N+(CH3)3Cl

Tetramethyl ammonium chloride

acetilcoline chloride

(Fessenden, 1976: 122-123) Acetanilide is converted to a phenolic metabolite in human body which gives it an analgesic effect, but some is converted to aniline (aminobenzene) which is toxic. It was found that for a single dose of 10 mg/kg of acetanilide. The half life in blood plasma was 191,5 +27,5 min of in 25 dose of 10mg/kg of acetanilide the half life in blood plasma was 191,5+27,8 min of in 25 subject (human) and the metabolic clearance rate was 14,1+2,8 liter/h of the structure formula is

(Oecd sid,2004:10) Benzothiazoles and N-Subtututed-o-chloro acetanilides have emerged as structurally novel anti oxidant activity. Therefore hydrazine benzothiazoles and acetanilide derivates on important class of medicinal compound. The search for antioxidant compounds with more selective and lower toxicity continues to be area of investigation in medical chemistry compounds containing a hydrazine benzothia zole, hydrazine benzothiazine and substituted chloro acetanilide component have shown a broad spectrum of chemotherapeutic properties including antimicrobial, antiviral anthelmentic, analgesics, until inflammatory and antycytotoxic activies of substituted acetanilides (Suresh, dkk. 2011: 409). R-NH2-R-C

R-C-N+H2R

R-C-NH-R+ x-

x= -OH, -OCOR or –Cl acetilation uses glacial acetalec acid that more cheap, although use long time. Because in last process there is equilibrium R-NH2+ CH3COOH

R-NH-C-CH3 + H2O

Then to get high result, equilibrium need to moved to right with lost the air and produced by distillation. (Tim dosen, 2012: 5-6). There are few simple of anilyn structure phenoylamate is qually call aniline

aniline Heterocyclic compound the nitrogen part of aring compound used as different heterocyclic ring like parent hame Pyridine

perin

(Mc Murry,2007:373). D. Apparatus and Chemicals 1. Apparatus a. Distillating flask 1 peace b. Reflux condenser 1 peace c. Thermometer 240oC 1 peace d. Volumetric glass 25 ml 2 pieces e. Buchner funnel and funnel 1 piece f. Wash bottle 1 piece g. Erlenmeyer 1 piece h. Beaker glass 100 ml 1 piece i. Stir bar 2 pieces j. Store and boiling stone 1 piece k. Rough and smooth cloth 1 piece l. Dropping pipette

2. Chemicals a. Aniline (C6H5NH2) b. Glasial acetic acid (CH3COOH) c. Actirated carbon/ norite d. Capiler pipe e. Alluminium foil f. Aquadest g. Alcohol h. Filtering paper i. Whatmann paper j. Ice cubes E. Work Procedure 1. Put into a round flask 25 ml acetic acid and 20 ml amine 2. Put same boiling stones into round flask and refluxed with temperature (104105oC) to 13,5 ml 3. After refluxed, then mixed into the ice tube in the residue (acetanilide) and stired to form a solid crystal alkine form 4. Heated to boiling and then diluted with alcohol and water then added norit 5. Filterated the solution with a Buchner filtered and conducted dirty acetanilide crystal solids 6. Solids acetanilide products of the synthesis was dissolved in again with alcohol and heated to boiling and then added norit to it 7. The solution filtered again with Buchner and then result put into beaker and filtered called used ice tube to obtain crystals acetanilide 8. Mixed a crystal is then filtered with filter paper 9. Dried of crystal more obtained from filtration ands measured weight and melting point F. Observation Result No Observation 1

Result

Measured aniline in volumetric 12,5 ml with red solution glass

2

Measured acetic acid in volumetric 10,00 ml transparanmt solution glass

3

Aniline + acetic acid + boiling Red mixture solution stone into round flask

4

Distillated

mixture

until Separated: 1) residue (acetanilide)

temperature 104oC

2) dustllate + H2O (yellow solution) Brown chunks + solvent

5

Filled the residue unto cool water

Separated -> transparent (filtrate)

6

Filtered the brown chunks

Residue (brown chunks)

7

Dissolved the residue with ethanol 20:20 ml ethanol and H2O + H2O

8

Added mixture with norite and Dark brown solution heated

9

Filtered dark brown solution with Separated -) turbid (filtrate) funnel

Dark brown chunks

10

Filled the filtrate into cold water

Until formed with crystal + solvent

11

Filtered the crystal with using Filtered, residue (crystal) funnel

Filtrate (solvent)

12

Put the crystal into the oven

Dry crystal (acetanilide)

13

Balanced the dry crystal

Pure acetanilide (1,5g)

14

Determine

melting

point

of 113-116oC

acetanilide crystal

G. Data Analysis Known = - V C6H5NH2 = 12,5 ml - V CH3COOH = 10 ml - Mr C6H5NH2 93 g/mol -Mr CH3COOH = 60 g/mol - Mr C6H5NHCOOCH3 = 135 g/mol

- p aniline = 1,022 g/ml - p CH3COOH = 1,049 g/ml Ask = rendemen? Mass of aniline

= (p x v) aniline = 1,022 g/ml . 12,5 ml = 12,775 g

Mass of CH3COOH = (p x v) CH3COOH = 1,049 g/ml . 10 ml = 10,49 g Mol of aniline

= = = 0,137 mol

Mol of CH3COOH = = = 0,17 mol C6H5NH2 + CH3COOH  CH3CONHC6 H5 + H2O M 0,137 mol 0,17 mol B 0,137 mol 0,137 mol

0,137 mol

0,137 mol

S -

0,137 mol

0,137 mol

0,033 mol

Theory mass of acetanilide = (mol x Mr) CH3CONHC6 H5 = 0,137 mol . 135 g/mol = 18,459 g Rendement =

x 100%

= 0,081 x 100 % = 8,1 %

H. Explanation In this experiment, acetanilide was made with react aniline as base material with glatial acetat acid solution. The aniline prepare a amine group therefore glatial acetat acid or pure acetat acid without other mixing. It function as preparer asetil group or reactant (nucleofil) that will be substitute by amine group and group which can move the other atom. This structure can move or release from its structure. Then this mixing was destilated in temperature 104-105oC to separate acetanilide with reaction side result which formed namely water. The temperature was kept in order not more or less from 104-105oC in order the acetanilide which formed not broken and the water can be out because boiling point of water is 100 oC. Before done distillation was entered boiling stone in the mixing prevent occur the explotion in heating. The distillate which be gotten in kept and the residue which be there is the cycle flask cold in cold water to fast formed of crystal. So it filtered with Buchner and result brown residue. Then added ethanol 1% and water. The adding of water 20 ml with purpose to dilute the sediment or crystal therefore ethanol purpose to dilute the crystal which yet diluted when adding of water, beside of that the ethanol also purpose to recrystallization and lost the dirty substances. Recrystallization purpose to get the acetanilide that be purer. Then added norit and heated, the function of norit to adsorb color. So, heated and filtered in heat condition. It thing in order to avoid formed the crystal when the solution was cold. After filtered, get the white crystal, then the crystal entered in the oven because the crystal still contain water. After dry the color of crystal is white, it suitable with theory that the crystal of acetanilide is white. The mass of acetanilide is 1,5 gr with rendement 8,1 %. After that done the test of melting point , got melting point of acetanilide is 113-116oC. It suitable with theory that melting point of acetanilide is 113,7oC The reaction is H N

H H

O

+

H 3C OH

N

H

O

+

H 3C

C

-

+

OH

H N

O

+

-

OH

H

H

O

-

N

CH3

OH

+

CH3

H

+

H N

H

O

+

H 3C

C

-

H

+

N H

OH H

O

OH

H

O

H

-

N

CH3

+

+

H

+

H

+

N

O

OH

CH3

+

HO

CH3

+

CH3

H +

-

-

-

N

O

-

N

Acetanilide

H

+

O CH3

+

HO

+

-

H 2O

water

I. Closing 1. Conclusion a. In this experiment rendement is 8,1% and the mass of acetanilide is 1,5 g. b. The preparation of acetanilide in acetalase process us a reaction between aniline with acetate acid product in the form of crystal purified by crystallization. 2. Suggestion a. Apperantice must be carefully to keep the temperature when distillation process. b. Apperantices must be carefully when filtering

BIBLIOGRAPHY

Fussenden. 1976. Kimia Organik Edisi Ketiga Jilid 2. Jakarta: Erlangga. Mc Murry. 2007. Fundamental of Organic Chemistry. London: Thomson Red Camprk. Decsids. 2004. Acetanilide. UNEP publications. Rasyid. 2009. Kimia Organik 1. Makassar: UNM. Suresh. 2011. Synthesis of 2-Hydrazinobenhotalzoles-2-aminos(4substiturted)acetanilides for antyoxidant Activity. India International Journal of Pharmacy and Biologycal Science. Tim Dosen. 2012. Penuntun Kimia Organik II. Makassar: UNM.