LABORATORY

MANUAL
CH3CH2OH

Nao

CH3CH2ONa

OH
CH3CH2ONa +

ONa

+ CH3CH2OH

ONa
CH3(CH2)3Br

+ 1/2 H2

ORGANIC
CHEMISTRY
YEAR TWO

O(CH2)3CH3

NaBr

Year 2

Organic Chemistry

Contents

ORGANIC CHEMISTRY
CONTENTS

Page
Radas Dengan Penyambung Kaca Yang Boleh Ditukarganti

Experiment 1

SN2 Reaction - Butil Fenil Eter

Experiment 2

Grignard Reaction - Triphenylcarbinol

Experiment 3

Diels-Alder Reaction

3.1 Reaction of cyclopentadiene with malic

anhydride

3.2 Reaction of Furan with Maleic Anhydride

Experiment 4

Separation of Piperine from Black Paper

Experiment 5

Stim Distillation of impure essential oil sample

11

Experiment 6

6.1 Beckmann-benzanilide rearrangement

13

6.2 Preparation of Caprolactam through

Beckmann rearrangement

14

Preparation of an Azo Dye: 1-(p-nitrophenylazo)-2naphthol

16

Qualitative Organic Analyis

18

Laboratory Notebooks

21

Experiment 7

Attachment

Year 2

Organic Chemistry

RADAS DENGAN PENYAMBUNG KACA YANG

BOLEH DITUKARGANTI
Penyambung kaca ground cepatsuai
Menjangkau suku pertama abad ini, cara yang terdapat untuk menyambung radas kaca
makmal ialah dengan menggunakan gabus, penyumbat getah, pembuluh getah dan
pembuluh kaca. Memasang benda-benda tersebut adalah rumit dan kadangkala
berbahaya dan selalunya memakan masa. Satu pembaharuan yang patut diperhatikan
datang dalam awal tahun 1930 apabila penyambung kaca ground berbentuk kun
diperkenalkan dalam arena perniagaan. Dengan cara asahan, kun dan soket dibuat
dengan tepat agar keduanya terhubung dengan cepat dan berkesan. Dengan itu nama
perniagaannya ialah cepatsuai.

Ukuran penyambung kaca

Terdapat 3 ukuran yang berlainan yang diakui oleh ukurtentu BSI, disediakan dalam satu
susunan lengkap radas cepatsuai iaitu, B24, B19, B14 dalam susunan garispusat
penyambung kaca dari besar ke kecil. Istilah kun digunakan sebagai bahagian yang
disisipkan dan soket digunakan sebagai bahagian yang menerima sisipan kun itu.

Penjagaan penyambung kaca ground

Semua penyambung kaca ground mesti disimpan supaya terhindar daripada kekotoran.
Habuk yang melekat pada penyambung kaca ground mungkin menyebabkan bocor
dan retak atau seterusnya pecah. Oleh sebab itu, sebagai satu aturan biasa sebelum ia
digunakan, penyambung kaca ground mesti disapu bersih dari sebarang bendasing.
Lepas digunakan penyambung kaca ground mesti dipisahkan secepat mungkin, lebihlebih lagi ketika masih panas untuk mengelakkan pengetatan.

Pengetatan
Ini berlaku apabila penyambung kaca ground menjadi ketat dan susah untuk dipisahkan
semula. Jangan biarkan soda api melekat pada permukaan penyambung kaca ground.
Ia bertindakbalas dengan pantas ke atas permukaan yang kesat itu dan ini
menyebabkan berlakunya pengetatan. Pengetatan juga boleh disebabkan oleh
sepitan.

Pelicinan
Dalam kerja pada tekanan udara, tiada pelicin harus digunakan. Tetapi apabila
menjalankan penyulingan di bawah tekanan udara yang rendah atau apabila terdapat
kemungkinan larutan alkali terkena bahagian permukaan penyambung kaca ground,
maka gris diperlukan sebagai pelicin. Kegunaan bahan pelicin bergantung kepada
keadaan radas yang dikendalikan. Biasanya petrolium jeli atau gris silikon stopcock
digunakan tetapi pelicin silikon vakum tinggi layak digunakan pada suhu yang tinggi,
dan kerja-kerja vakum. Cuma satu lapisan nipis pelicin sahaja perlu digunakan. Jika

Year 2

Organic Chemistry

berlebihan, ia akan mengotori hasil tindakbalas. Apabila menggunakan gris silikon,

hendaklah cermat kerana perkakas yang bersambung tidak boleh ditinggal terbiar
beberapa lama kerana jika pelicin menjadi kering, pengetatan penyambung kaca akan
terjadi.
Untuk menanggalkan silikon dari penyambung, sapulah sehingga kering dengan sehelai
kertas tisu, dan gris yang tertinggal kemudian ditanggalkan dengan segumpal bulu
kapas yang dibasahi dengan eter atau kloroform.

Penyambung kaca terangsuai

Penyambung kaca ground kun mempunyai kekurangan yang tak dapat dielakkan
kerana apabila permukaan licin asli itu dibinasa oleh asahan, beberapa
keistimewaannya akan hilang. Kemajuan terbaharu dalam teknik pengeluaran telah
membolehkan dicipta satu jenis perkakas baharu makmal yang boleh ditukarganti
dengan penyambung kaca kun yang terang dimana permukaan kaca yang mulanya licin
tersimpan dan dinamakan terangsuai.
Penyambung terangsuai mempunyai lebih keistimewaan daripada penyambung ground
seperti berikut: (a) Pelicin tidak perlu dalam semua kerja. (b) Buatannya yang teliti,
permukaan penyambung terangsuai memberi meterai yang lebih baik dari penyambung
kaca ground dan kurangkan keupayaan wap terkondensasi dan menjalar di antara
permukaan penyambung oleh tindakan rerambut. (c) Kurang berbahaya terhadap
pengetatan kerana penyambung terangsuai dimeterai dengan baik. Oleh itu, larutan
beralkali boleh dielakkan daripada meresap ke dalam penyambung. (d) Permukaan asli
yang licin terdapat penahanan minima terhadap benda-benda yang mengotori
permukaan penyambung terangsuai yang bersentuhan. (e) Penyambung terangsuai
memberi pemeteraian vakum yang baik. Untuk vakum maksima, pelicinan ringan pada
penyambung adalah perlu. (f) Kekuatan mekanikal penyambung terangsuai adalah lebih
besar dari penyambung dasar kerana apabila penyambung kaca dilaraskan ada
kemungkinan terjadinya retakan kecil yang boleh melemahkan penyambung. (g) Radas
yang dipasang dengan penyambung terangsuai adalah lutsinar termasuk permukaan
penyambung itu. Semua perubahan kimia, skala jangkasuhu kekal sepenuhnya dapat
dilihat melalui penyambung itu. Harga perkakas kaca terangsuai adalah lebih mahal dari
cepatsuai.

Pengapitan perkakas kaca cepatsuai dan terangsuai

Oleh kerana penyambung kun adalah teguh, cuma satu pengapit dikenakan pada
sebuah radas dengan cermat. Lebihan sokongan kepada pengapitan sebagai satu
prinsip dalam penyusunan perkakas kaca. Pengapit cuma mesti diketatkan kepada
ketatan-hujung jari sebelum pengapit itu diketatkan pada sokong, mula-mula mesti
periksa yang radas bebas dari tegangan fizikal.

ii

Year 2

Organic Chemistry

Pembersihan perkakas kaca

Membersih hingga kering radas adalah satu keperluan dalam praktikal kimia organik.
Perkakas kaca mesti dicuci dengan air sabun yang panas atau bahan pembersih
(Teepol). Jika pembasuhan dilakukan dengan cepat mungkin selepas selesai satu-satu
percubaan, adalah lebih mudah menanggalkan sebatian organan yang terlekat pada
radas gelas itu. Jika berus digunakan di dalam kelalang adalah mustahak bahagian
logam dilindungi rapat untuk mengelakkan sebarang calaran. Pelarut organik jangan
selalu digunakan, cuma apabila cara lain tidak berkesan. Bila bertar boleh dikeluarkan
dengan menggunakan campuran pembersih dikromat. Bila radas kaca telah bersih dan
bebas daripada gris, ia cepat kering kerana air tidak terkumpul dalam titik-titik. Adalah
baik ditinggalkan di dalam satu rak supaya air mengalir keluar atau ia boleh dikeringkan
dalam satu oben. Pengeringan dengan cepat boleh dilakukan dengan menggunakan
penyembur udara panas. Perhatian istimewa diberi dalam meletakkan perkakas kaca
pada hujung penyembur kerana getaran boleh menyebabkan retakan kecil ke atas
permukaan kaca. Bahagian luar radas kaca mesti selalu dikeringkan dan digilap
dengan kain kaca; cuma setelah diluarnya bersih, dapat diketahui keadaan di dalamnya.

Calaran
Perhatian mesti diberi untuk mengelakkan calaran ke atas permukaan perkakas kaca.
Jika tidak ini mengurangkan kekuatan mekanikal ke atas permukaan kaca yang
menyenangkan pecahan melalui kejutan haba, istimewa bila calaran terdapat di
bahagian dalam permukaan kaca. Hati-hati dalam pemegangan, pembasuhan dan
penyimpanan kelalang-kelalang, akan membolehkannya digunakan lebih lama. Calaran
cukup untuk menyebabkan pecahan, didapati dengan pengacau kaca yang tidak
dilindungi getah, dengan geseran atau ketokan antara dua kelalang atau dengan batang
logam berus pembersih. Teknik calaran dengan pembuluh kaca untuk menggalakkan
penghabluran jangan sekali dijalankan di dalam satu kelalang cepatsuai atau terangsuai.

iii

Year 2

Organic Chemistry

Experiment 1

EXPERIMENT 1
SN2 REACTION - BUTYL PHENYL ETHER
Alkyl halides can undergo a general reaction as indicated in the following:

R-X

Nu :

X-

R-Nu

Two examples are shown as follows:

CH3Cl

CH3CH2Br

OH -

CH3OH

Cl -

+ Br -

CH3CH2OCH3

OCH3

In this reaction, a species having an unshared pair of electron called nucleophile, reacts with an
alkyl halide to replace the substituent; halogen. Substitution reaction has occurred and the
halogen leaves as a halide ion. Thus this reaction is called the nucleophilic substitution reaction.
The carbon-halogen bond may be cleaved before or during the formation of the new bond
between the carbon and the nucleophile. This depends on the structure of the alkyl halide
involved in the reaction.
Primary alkyl halides undergo bimolecular nucleophilic substitution reaction, SN2. In this
experiment, n-butyl phenyl ether is prepared through SN2 reaction, between n-butyl bromide with
phenoxide ion. As phenol is more acidic than ethanol (or water), it is added to sodium ethoxide in
absolute ethanol and then the phenoxide ion formed is left to react with the alkyl halide.
o

CH3CH2OH

CH3CH2ONa

Na

OH
CH3CH2ONa

ONa

ONa
CH3(CH2)3Br

1/2 H2

CH3CH2OH

O(CH2)3CH3

NaBr

Apparratus
2 necked round bottom flask,250 ml
B14/B19 and B19/B24
Drying tube CaCl2

Reduction adapters B19/B24

Water-condenser
Separating funnel

Chemicals
1.9g sodium
7.8g phenol AR

Absolute ethanol
n-butyl bromide (13ml, 16.6g)

Year 2

Organic Chemistry

Experiment 1

Method
All apparatus must be dried. Prepare the apparatus as depicted in figure III(Appendix), and add
44ml of absolute ethanol. Cut 1.9g sodium ( note 1) into 3 or 4 pieces, and add all the pieces into
the reaction flask. ( cool the flask in waterbath to make sure the ethanol is refluxed slowly, if
needed ). After all the sodium has dissolved , add 7.8g phenol (note 2) in absolute ethanol (10ml)
into the reaction flask and then mix the mixture thoroughly. Add n-butyl bromide through a dropper
funnel in 1 minute and heat the flask in a waterbath and left to reflux for 15 minutes. Remove
excess ethanol by distillation. Then, pour 20ml water into the cold reaction flask (note 3). Then
transfer the mixture into a separating funnel. Wash the organic layer with 10% NaOH solution
(2x5ml). (Do not shake too strongly as emulsion may be formed !!!!). Then wash the organic layer
with 10% H2SO4 solution followed by water. After that, add anhydrous MgSO4 to dry the organic
layer (note 3). Pour the filtered organic layer into a pear shaped 25ml flask. Finally, distill the
compound using an air-bath. State the boiling point and weight of the n-butyl phenyl ether
obtained.

Note
1.

All the safety procedures must be followed while conducting sodium. Lab
assistant will do the measurements. Prepare all apparatus needed before taking the
sodium! ( Sodium can be replaced by potassium hydroxide, 4.9g. Weigh
hygroscopic material immediately).

2.

Chemicals are dangerous. Beware of your skin !!!!

3.

If time is limited, stop here.

Question
1.

Why must the excess alcohol be separated ?

2.

If (R)-2-bromobutane reacted with phenoxide ion through SN2 reaction, what

will be the expected product. State the stereochemistry of the compound. (Draw
the structure of the compound with the correct stereochemistry).

Year 2

Organic Chemistry

Experiment 2

EXPERIMENT 2

GRIGNARD REACTION-PREPARATION OF
TRIPHENYLCARBINOL

An example of a class of reaction that involves a formation of a new carbon-carbon bond in the
carbon skeleton of a molecule is the Grignard reaction. In 1912, Victor Grignard (University Of
Lyons, France) was awarded the Nobel Prize in Chemistry for the discovery of the Grignard
reaction. The Grignard reaction is typical class of "organometallic" reaction in which a Grignard
reagent acts as a source of nucleophilic carbon reacting with a relatively electron deficient or
electropositive carbon, typically an aldehyde, ketone or organic ester. In general, Grignard
reagent is prepared by reacting an organic halide with magnesium metal in dry ether or THF.

RX

Mg

Dry Ether or THF

RMgX

A Grignard reagent has a formula RMgX where X is a halogen, and R is an alkyl or aryl group.
Since the Grignard reagent is very reactive, it will also attack any of a large variety of acidic or
electropositive reagents.
The Grignard reaction involves a nucleophilic attack of a carbanion (the Grignard reagent) on a
carbonyl carbon. The C=O pi-bond is broken and a new carbon-carbon bond is formed between
the Grignard reagent and the carbonyl carbon. Upon hydrolysis, an alcohol is isolated as the
product.
This experiment aims to prepare triphenylcarbinol through a Grignard reaction by reacting
methylbenzoate with phenylmagnesium bromide as shown in the scheme below:

2C6H5MgBr

+ Ph

OMgBr
OCH3

Ph

Ph

Ph

MgBrOCH3

Ph
OMgBr
Ph

C
Ph

Ph

OH

H3O

Ph

MgBrOH

Ph

Year 2

Organic Chemistry

Experiment 2

Procedure

Placed about 1.4 g of magnesium turnings and sodium-dried ether (enough to cover the
magnesium turnings, about 10 mL) in a dry 250 mL two-necked flask fitted with a 50 mL dropping
funnel and a reflux condenser (all apparatus must be completely dry). Place a drying tube filled
with calcium chloride at the top of the condenser. This is to prevent the entrance of moisture
through the condenser and the dropping funnel during the addition.
Into the dropping funnel, place a mixture of bromobenzene (9.2 g, 6.2 mL) in dried ether (30 mL).
Run in a small amount of the mixture of bromobenzene in ether (about 5 mL) slowly into the
reaction flask and shake the flask gently. Add one or two iodine crystal as catalyst to initiate the
reaction. If the reaction does not start after 2-3 minute (iodine color dissappears, cloudy solution is
formed, and ether solution start to boil) warm the reaction flask gently (use water bath) until the
reaction start on its own, then remove the water bath (if the reaction still does not start, use
ultrasonic or add 1 mL of Grignard reagent prepared by lab assistant). When the reaction has
started (not before), add the rest of the mixture of bromobenzene in dry ether into the reaction
vessel at such a rate as to cause refluxing (cool in ice-bath if the reflux becomes to vigourous).
When the addition is completed, continue refluxing the solution on water bath for another 15
minute to ensure that the reaction is complete. At this point, there should not be any magnesium
left. Cool the reaction mixture to room temperature or below.
To the Grignard solution, 3.5 g (3.2 mL) of methyl benzoate in 10 mL dry ether is added
(through a dropping funnel) at such a rate that the mixture refluxes gently (within 20 minute). From
time to time shake the flask gently to ensure the reaction mixture mix throughly. After the addition
is completed, the mixture is refluxed for about 10-15 min on a steam bath. The reaction mixture is
cooled in an ice bath and then poured slowly, with constant stirring, into a 600 mL beaker contains
mixture of 75 g of cracked ice and 30 mL 10% aqueous sulfuric acid. The mixture is stirred until
all the solid has dissolved. If necessary, additional ether may be added if the amount present is
insufficient to dissolve all the product. When the solids have completely dissolved, the ether layer
is transferred into separating funnel. Remove the bottom layer (aqueous) and wash the ether
layer, successively with 15 mL 10% aqueous H2SO4, 12 mL water and finally with 1 g sodium
bisulfite in 12 mL water. The solution is dried with anhydrous Na2SO4. Filter and add 15 mL
petroleum ether (60-80) to the ethereal solution. Concentrate the solution gently on steam bath
until triphenylcarbinol crystal start to come out. Leave the mixture to cool to room temperature
o

then place the flask into an ice-bath (0 C) to ensure all the triphenylcarbinol has crystallized out.
The crude triphenylcarbinol is recrystallized from methyl spirit (4 mL of solvent per gram of solid).
Weight of the dried crystals, take the melting point and calculate the total yield of triphenylcarbinol
obtained.

Year 2

Organic Chemistry

Experiment 2

QUESTIONS:
1.

Why must all the apparatus used in the reaction be completely dry?

2.

Compare the molar quantities of magnesium, bromobenzene and methyl benzoate used
and explain the sense to the specified reactant ratios.

3.

How does using ether solvent help decrease the formation of the by-products resulting
from reaction with oxygen and carbon dioxide of the atmosphere?

4.

NaHSO3 solution is used in the work-up to remove iodine used as catalyst early in the
reaction? Write the equation for what happened between iodine and NaHSO3.

References:

1. Techniques & Experiments for Organic Chemistry, Ault, Addison, 6th Edition,
University Science Books, 1997
2. W. E. Bachmann and H. P. Hetzner, Organic Syntheses, CV 3, 839

3. Org. Syn. Coll. Vol. 3, 841

4. Operational Organic Chemistry: A Problem-Solving Approach to the Laboratory
rd

Course, John W. Lehman, Prentice Hall; 3 edition, 1998

Tahap 2

Kimia Organik

Eksperimen 3

EXPERIMENT 3
Diels-Alder Reaction
Background
The formation of new carbon-carbon bonds is one of the most important aspects of
synthetic organic chemistry. Many reactions, such as the Grignard reaction and the use
of acetylide ions in SN2 reactions, have been developed with this one goal in mind. One
problem associated with most of these CC bond-forming reactions is the necessity for
exotic conditions the Grignard reaction requires completely water-free conditions and
acetylide ions must be generated in liquid ammonia solution.
When a synthetic sequence calls for the formation of a ring of carbon atoms, this
problem is compounded. Fortunately, the formation of six-membered carbon rings is
much simpler than it would first appear. As described in Organic Chemistry by Carey
(Section 10.12), the Diels-Alder reaction was discovered in 1928. This reaction forms a
six-membered ring from two pieces: a conjugated "diene" (which provides four of the ring
atoms) and a "dieneophile" (which provides two of the ring atoms). The main
requirements for these species are that the conjugated diene must be somewhat
electron rich (which is normally the case for dienes) and able to achieve the s-cis
conformation, and that the "dieneophile" have a two-atom system that is relatively
electron poor.
In this experiment you will react cyclopentadiene (the diene) with maleic anhydride (the
dienophile) to produce the bicyclic compound, endo-bicyclo[2.2.1]hept-5-ene-2,3dicarboxylic anhydride. The endo-adduct is formed exclusively. Why?
O

H
H

O
H

exo-

endo-

One important aspect of this experiment is that the cyclopentadiene must be freshly
distilled within one day before the reaction is carried out. Why? Answer at end of
experiment!
Experiment 3.1
Reaction of cyclopentadiene with maleic anhydride
Procedure
Part A: Distillation of Cyclopentadiene.
Place dicyclopentadiene (10 mL) in a 25 mL round-bottomed flask (in the fumehood).
Complete the set-up with a Vigreux column (for fractional distillation), an adapter and a
condenser for distillation. Heat the dicyclopentadiene on a hot-plate until it refluxes
briskly. The monomeric cyclopentadiene should start to distill within a few minutes.
Continue to heat the dimer reagent to promote fairly rapid distillation and collect the
cyclopentadiene into a receiver flask which is cooled to 0 oC using an ice-water bath.

Tahap 2

Kimia Organik

Eksperimen 3

(Note 1). Do not allow the distillation temperature to exceed about 45oC, which is
slightly above the boiling point of cyclopentadiene (40-43oC).
After all the cyclopentadiene has been collected, stop the distillation and discard the
unused residue from the reaction flask, into the liquid waste container. If the
cyclopentadiene is cloudy, add a few pieces of anhydrous sodium sulfate (or anhydrous
magnesium sulfate). Decant the dry cyclopentadiene from the drying agent for use in the
experiment below.
Part B: Diels-Alder Reaction
Grind 5 g maleic anhydride using a small mortar and pestle to break up any chunks, and
dissolve it in 20 mL of ethyl acetate (you may need to heat it) in a 125-ml Erlenmeyer
flask. Once the maleic anhydride is dissolved, add 20 mL of petroleum ether and place
the solution in an ice bath to cool to well below room temperature. Add (in the hood)
about 5 mL of the freshly distilled cyclopentadiene directly to the cold maleic anhydride
solution (if the solution contains any crystals, dissolve them before adding the
cyclopentadiene). Swirl the reaction mixture in an ice bath until the product has finished
precipitating.
After crystals have formed, recrystallize your product by simply heating the product
mixture on a hot plate until the solid dissolves (but do not boil). Allow the solution to cool
at room temperature until recrystallization has finished. Collect the crystals using a
Bchner funnel. (If you have crystals still present in the flask, do not use water to wash
the crystals, as the acid anhydride will react; use the filtrate (mother liquor) to wash the
flask. Collect as much crystals as possible.
NOTE 1: Safety
Cyclopentadiene (and its dimer, dicyclopentadiene) is an irritant, is flammable, has an
unpleasant odor and is harmful if inhaled avoid breathing its vapors. No flames will be
allowed in the lab. Wear gloves while handling these chemicals. Dispense and use
these chemicals in the hood to minimize inhalation hazards.
Maleic anhydride is corrosive and toxic--wear gloves while handling it. Be sure to wash
your gloves and your hands after handling it.
Questions:
1. How many new bonds, and of what type ( or ), are created in a Diels-Alder
reaction?
2. What is the theoretical yield of product, based on the amount of
cyclopentadiene used in the experiment.
3. What is the structure of the dicyclopentadiene?
Experiment 3.2
Reaction of Furan with Maleic Anhydride
The objective of this experiment is to perform a Diels-Alder reaction between the furan
and maleic anhydride.

Tahap 2

Kimia Organik

Eksperimen 3
O

Endo or Exo Adduct?

Procedure:
Prepare 10 mL of a 4M solution of maleic anhydride in CH2Cl2. (Use the calculations in
your lab notebook). Filter off the insoluble maleic acid using a Hirsch funnel and suction
filtration. Measure 1 mL furan into a test-tube and add the appropriate equimolar amount
of maleic anhydride to the reaction tubes (use calculations in prelab). Cork the test
tubes, seal the corks with Parafilm, and set them in your locker until the next laboratory
period because the reaction takes 24 - 48 hours to reach completion.
(Progress of reaction could be monitored through TLC. The TLC plate should have three
spots (or lanes) on the origin: one for the main organic starting material that is being
transformed, one for a co-spot (starting material and the reaction mixture), and one for
the reaction mixture).
Isolation and Purification:
If crystals haven't formed, insert a clean stirring rod or boiling stick into the reaction tube,
remove the wet rod or stick, and allow it to dry, forming seed crystals. When reinserted,
crystallization should be instantaneous. Pipet off the remaining liquid, wash the crystals
with ice-cold CH2Cl2 or 1:1 (V/V) CH2Cl2:hexane, let the crystals dry, and determine the
yield and melting point.
Take the melting point of the furan adduct before recrystallization. Use a 5:2 mixture of
hexane:ethyl acetate to dissolve only part of the crude product and place the flask in hot
water bath. The temperature of the water bath should be adjusted to just below the
melting point obtained to dissolve the adduct. Alternatively, acetone could be used as
the solvent for recrystallisation and crystallization could be induced by dripping hexane
into the acetone solution. Obtain melting points of all recrystallized products.
The furan adduct requires much more "finesse" to recrystallize since it undergoes a
reverse or retro Diels-Alder reaction at the melting point.
Caution:
Maleic anhydride and the Diels-Alder adducts are intense skin irritants Furan is very low
boiling.
Questions:
1. Determine which of the possible products were produced, exo or endo, by comparing
your melting points with the literature values.
2. How would you prepare 5 mL of a 4M solution of maleic anhydride in CH2Cl2? Show
calculations.
3. How many moles are in 0.5 mL furan? How many mL of the 4M maleic anhydride in
CH2Cl2 would be an equimolar amount?

Tahap 2

Kimia Organik

Eksperimen 3

4. Explain why the 4M solution of maleic anhydride is made in CH2Cl2 and not in water.
Show the reaction between maleic anhydride and water.
5. Give structures for the major Diels-Alder product of the following reactions:
1,3-cyclohexadiene and tetrachloroethene 1,3-cylcohexadiene and fumaric acid, the
trans isomer of maleic acid.
References:
References:
1. Techniques & Experiments for Organic Chemistry, Ault, Addison, 6th Edition,
University Science Books, 1997.
2. Operational Organic Chemistry: A Problem-Solving Approach to the Laboratory
Course, John W. Lehman, Prentice Hall; 3rd edition, 1998.

Year 2

Organic Chemistry

Experiment 4

EXPERIMENT 4
SEPARATION OF PIPERINE FROM BLACK PEPPER
Some of the organic compounds found in nature have specific smell or odour and they are usually
known, in general, as aromatic compound. In the early days, aromatic compounds meant then
that the compound had a low hydrogen/carbon ratio and that it was fragrant. The parent
compound of the aromatics is benzene. Today, not all aromatic compounds are fragrant but they
are called aromatic compounds because of their structure. Some examples of aromatic
compounds that have specific smell are vanillin (1) and safrol (2).

CH2CH=CH

CHO

OCH3

OH

(1)

(2)

Vanillin is obtained from vanilla and is widely used as deodorant, food flavour and one of the
ingredients in pharmaceutical products. A related compound is bourbonal (3) or 3-ethoxy-4hydroxibenzaldehyde while safrol can be obtained from sasafras and camphor oil. Piperonal (4) is
derived from safrol through isomerization to isosafrol followed by oxidation. Piperonal is used as
flavour in soap and deodorant because of its sweet smell.

CHO

CHO

OCH2CH3

OH

(3)

(4)

One of the spice which is widely known is black pepper or Piper nigrum . It has a rather hot and
sharp taste. This is due to the presence of piperine (5). Piperine has a unit of methylenedioxy as
in safrol and piperonal.

O
CH

CH

CH

CH

O
O

(5)

Year 2

Organic Chemistry

Experiment 4

Separation method
Extract the grounded black pepper (20g) with 95% ethanol (150ml) in a Soxhlet extractor for 2
hours. Filter the mixture and concentrate it in vacuum using rotary evaporator. Add an alcoholic
potassium hydroxide solution (10%, 10ml) to the concentrated filtrate. Then separate the solution
from the undissolved solid filtrate by slanting the flask. Leave the alcoholic solution for a night.
Piperine will be obtained as yellow needles. Collect the crystals by suction filtration.
Take the melting point and calculate the percentage yield. Record the UV spectrum (in ethanol)
and IR spectrum (disk KBr) piperine.

Thin Layer Chromatography

Dissolve a small amount of piperine in acetone and blotch it on the thin layer chromatography
plate ( silica gel Merck 60,F254). Place the TLC plate in a chromatography tank and develop it
using toluene-ethyl acetate solution (volume/volume 2:1). Place the plate under UV light (UV365)
and take note of your observation and the Rf value of the sample.
Reference
1.

Operational Organic Chemistry, A Laboratory Course, Second Edition, John W.

Lehman, Allyn and Bacon, 1988.

2.

Organic Chemistry, Volume 2: Stereochemistry and the Chemistry of Natural

Products, Fifth Edition, I.L.Finar, Longman, 1989.

3.

Natural Products, A Laboratory Course, Second Edition, Raphael Ikan,

Academic Press, 1991.

Question
1.

Why was 10% potassium hydroxide solution added to the filtrate ?

2.

What are the compounds that will be formed when piperine is hydrolysed with
potassium hydroxide in alcohol solution?

3.

Besides using UV light, what other method can be used to detect piperine.

4.

Predict the H NMR spectrum for piperine.

10

Year 2

Organic Chemistry

Experiment 5

EXPERIMENT 5
STEAM DISTILLATION OF IMPURE ESSENTIAL OIL SAMPLE
Introduction
Volatile compounds that are present in a mixture with the non-volatiles may be separated using
steam distillation. This can be achieved by exposing the mixture to steam. The volatile
components will then be extracted out from the mixture and follow the flow of the steam. For
example, o-nitrophenol can be separated from p-nitrophenol by using this method. Essential oils
from plants can also be separated from the plant aqueous mixture by steam distillation.
You will be given a mixture (X, Y, Z, etc.) which contain an essential oil sample such as limonene
(lemon), citronelal (lemongrass), isoeugenol (nutmeg), cineol (eucalyptus oil) and many others.
The mixture will consist of about 15% essential oil and 85% mixing agent; filtered of palm oil,
which has been discoloured and deodorized ( or r.b.d. refined, bleached, deodorized). The
essential oil can be separated from the mixing agent by using steam distillation.

Formula and IR Spectrum

IR spectrum (intensity)

CH3
CH3

O-H stretch 3500 cm-1 (moderate,wide)

C=C and stretch benzene 1597 cm-1 (moderate,wide)

CH=CHCH3
iso-eugenol (buah pala)

CH3

CH2

stretch 1650 cm-1 (medium)

H
C

bending 890 cm

-1

(strong)

H
H3C

CH2

limonen [(S) lemon, (R) oren]

11

Year 2

Organic Chemistry

Experiment 5

CHCHO
C=CH-CHO
CH3

Stretch 1650 cm-1 (strong)

for conjugated C=O

stretch of C-H aldehyde 2750 cm-1 and 2850 cm-1 (weak)

H3C

CH3

sitral (serai)

C=C non conjugated 1645 cm-1 (weak)

C=C conjugated 1625 cm-1

OH
OCH3

O-H 3500 cm-1 (moderate, wide)

C=C 1640 cm-1 (moderate)

CH2CH=CH2
eugenol

Chemicals
Sample W, X, Y or Z containing palm oil (r.b.d) and essential oil
Diethyl ether 10 ml
Sodium sulphate

Method
Prepare the apparatus as in figure VI. Take one sample (10g) oil mixture (W, X, Y, Z etc) and add
it into the flask. The steam distilled product will have two layers: aqueous and organic; essential
oil. Pour the product into the separatory funnel. Add NaCl to the product, then extract the essential
oil with 30 ml diethyl ether. Separate the ether layer, and dry it with anhydrous sodium sulphate.
Filter the mixture using cotton and distill the ether out (using water-bath). Weigh the essential oil
obtained and give to the lab assistant for further analysis.
Identification of the oil can be made from its odour. Use IR spectrum to confirm its structure. Note
-1
the absorption reading (cm ) for your sample.

Question
1.

o-hydroxybenzaldehyde can be separated from p-hydrobenzaldehyde by steam

distillation. Compare the structures of o-nitrophenol and p-nitrophenol. Suggest the
factor/s that makes o-nitrophenol more volatile the p-nitrophenol based on their
structures ?

2.

Draw the structures of R&S-limonenes.

3.

How do you differentiate the R&S limonenes?

12

Year 2

Organic Chemistry

Experiment 6
EXPERIMENT 6

6.1

BECKMAN-BENZANILIDE REARRANGEMENT

Condensation of a ketone with hydroxylamine hydrochloride in the presence of excess

sodium hydroxide solution forms a ketoxime.
R2C=O + NH2OH.HCl + NaOH

R2C=NOH + NaCl + 2H2O

Reaction of an ethereal solution of an oxime with either phosphorus pentachloride or

thionyl chloride gives an amide, a product which is formed through a rearrangement
reaction.
R'

SOCl2 or

C N
R

OH

PCl5

HO

C N
R

R'

NHR'

Conversion of any oximes to substituted amides in the same reaction condition as

mentioned above is known as Beckmann rearrangement. The reaction involves the
formation of an electron-deficient nitrogen atom, followed by a migration/shift, normally
involves a migration of an alkyl group to the electron deficient centre. This is an example
of a reaction that involves a 1, 2- shift/migration.
Apparatus
Round-borttomed flask B19, 50 mL Condenser B19
Vacuum desiccator
Round-borttomed flask B19, 100 mL
Still-head B19/19/14
Beaker 250 mL
Chemicals
2.5 g benzophenone
20 mL diethyl ether (anhydrous)
1.5 g hydroxylamine hydrochloride

7.5 mL conc. hydrochloric acid

2.8 g sodium hydroxide pellets
5 mL rectified spirit

Method
(a) Preparation of benzophenone oxime
Place a mixture of 2.5 g benzophenone, 1.5 g hydroxylamine hydrochloride, 5 mL
rectified spirit and 1 mL of water in a 50 mL round-bottomed flask. Add 2.8 g of
sodium hydroxide pellets in portions with shaking; if the reaction becomes too
vigorous, cool the flask with running tap water. When all the sodium hydroxide pellets
has been added, attach a reflux condenser to the flask, heat to boiling and reflux for
5 minutes. Cool and pour the contents of the flask into a solution of 7.5 mL of
concentrated hydrochloric acid in 50 mL of water contained in a 250 mL beaker.
Filter the precipitate at the pump, wash thoroughly with cold water and dried.
Recrystallise the precipitate from methanol and record the weight of the product, and
its melting point. (Note: The oxime is gradually decomposed by oxygen and traces of
moisture into benzophenone and nitric acid; it should be kept in a vacuum desiccator
filled with pure dry carbon dioxide or nitrogen).

13

Year 2

Organic Chemistry

Experiment 6

(b) Beckmann Rearrangement of benzophenone oxime (Note 1)

Dissolve 2 g of benzophenone (prepared in (i)) in 20 mL of anhydrous ether in a 100
mL, B 19 round-bottomed flask (all the apparatus must be dried!!) and add 3 mL of
pure thionyl chloride (this step should be carried out in a fume cupboard). Distill of
the solvent or other volatile products (as shown in Diagram V) on a water bath. Add
25 mL of water, boil for several minutes and break up any lumps which may be
formed. Decant the supernatant liquid (filter at the pump if necessary), and
recrystallise the product from methanol (toxic!). Record the weight of the product and
its melting point.
Exercise
1. Condensation of a ketone with hydroxylamine hydroxide in the presence of
sodium hydroxide gives a ketoxime. Can the reaction occur in the absence of
sodium hydroxide? Suggest explanations.
2. Suggest the product formed from the rearrangement of sulphuric acid induced
cycloheptanone oxime?
3. Suggest the mechanism of the following reaction:Ph

OH
C N

MePh

SOCl2

H2O

C6H5

NH
PhMe

Note 1:
All apparatus must be dried. Use thionyl chloride (SOCl2) in a fume cupboard, cool
the flask containing diethyl ether before adding thionyl chloride.
References
1. Elementary Practical Organic Chemistry Pt 1: Small scale Prepparation by A.I
Vogel.
2. Laboratory text in organioc chemisrry by Cason & Rapport
3. Laboratory Experiments in organic chemistry by Adams, Johnson, Wilcox.

6.2

PREPARATION
OF
CAPROLACTAM
REARRANGEMENT REACTION

THROUGH

BECKMANN

Preparation of Cyclohexanone oxime

Dissolve 7.5 g of hydroxylamine hydrochloride and 12 g of sodium acetate crystals in 30
mL of water in a 100 ML conical flask. Heat the reaction mixture to 40oC and add 7.5 g of
cyclohexanone. Stopper the flask and shake vigorously for 10 minutes. Oxime will
separate as crystalline solids, cool the flask in an ice bath. Filter the solid at the pump
and wash with cold water, Recrystallise oxime from petroleum-ether (60-80oC) and dry
the crystal in the air using a filter paper. Record the melting point and percentage of the
product obtained. Interpret the infra red spectrum of your product. ( Lit.; mpt.of

14

Year 2

Organic Chemistry

Experiment 6

cyclohexanone oxime 89-90oC).

Preparation of Caprolactam
Place10 mL of concentrated sulphuric acid in a 500 mL beaker. While stirring, slowly
add 5 g of cyclohexanone oxime to the mixture. (Carry out this process in a fume
cupboard because the reaction is exothermic and liberates heat. If heat is not liberated,
heat the mixture on a steam bath for 5 minutes). Let the reaction subsides, and then cool
the beaker in an ice-bath. Pour the reaction mixture into a beaker containing 150 g of ice.
Cool the beaker in an ice-bath, and slowly add potassium hydroxide solution (25%) until
the mixture becomes alkaline. Make sure that the temperature of the reaction is not
exceeding 10oC. (If precipitate of potassium sulphate formed, add water or filter the
precipitate, wash with dichloromethane and combine the dichloromethane wash with
dichloromethane extracts). Extract the alkaline solution with dichloromethane (3 x 75
mL), wash the dichloromethane layer with water and dried over anhydrous magnesium
sulphate. Remove the solvent using rotary evaporator, and extract crude oily product with
boiling petroleum ether (60-80 oC). Cool the petroleum-ether extracts and caprolactam
will crystallize out as colourless crystals. Record the melting point and percentage of
product obtained. Interpret the infrared spectrum of your product.
(Note: Hydroxylamine is very toxic and be careful when handling it)
Exercise
1. What is the role of sodium acetate in the formation of oxime?
2. Write a mechanism for the formation of cyclohexanone oxime.
3. What is the function of adding potassium hydroxide (25%) to the acidified
reaction products of cyclohexanone oxime?

15

Year 2

Organic Chemistry

Experiment 7

EXPERIMENT 7
Preparation of an Azo Dye: 1-(p-nitophenylazo)-2-naphthol
Background
The azo class of compound accounts for 60-70% of all dyes. Azo dyes are dyes with N=N- azo structure which links two sp2 hybridised carbon atoms. Usually, these carbons
are part of an aromatic system, although this is not always the case. Most azo dyes
contain only one azo group, but others may contain two (disazo), three (trisazo) or more.
In theory, azo dyes can supply a complete rainbow of colours. However, commercially
they tend to supply more yellows, oranges and reds than any other colours though there
are now some viable blue azo dyes on the market.
The general formula for making an azo dye requires two organic compounds- a coupling
component and a diazo component. Since these can be altered considerably, an
enormous range of possible dyes are available, especially as the starting molecules are
readily available and cheap. Furthermore, the simplicity of the reactions mean that the
process can be scaled up or down very easily, which is always a key factor in the cost of
chemicals. Energy requirements for the reaction are low, since most of the chemistry
occurs at or below room temperature. The environmental impact is reduced by the fact
that all reactions are carried out in water, which is easy and cheap to obtain, clean and
dispose of. As other dye classes become less viable from either an environmental or
economic reasons, azo dyes become ever more attractive options.
1-(p-nitophenylazo)-2-naphthol or Para Red is an example of an azo dye. This
intense orange-red dye was discovered in 1880 by von Gallois and Ullrich, and was the
first azo dye made. It dyes cellulose fabrics a brilliant red, but is not very fast.
NO2

+
N N: ClOH

N
+
N
OH
NO2

Procedure:
Part A: Preparation of p-nitrobenzendiazonium sulfate.
Dilute 2.0 mL (0.036 mol) concentrated sulfuric acid to 10 mL distilled water. Add 1.4 g
(~0.01 mol) p-nitroanile and heat the solution slowly till all the amine has dissolved. Cool
the solution to 10 oC in a ice-bath. While stirring, add 0.7 g (0.01 mol) sodium nitrite
(dissolved) in 2 mL distilled water slowly into the solution of p-nitroaniline sulfate that was
prepared earlier. Ensure that the temperation of the reaction does not rise to higher than
10 oC during the addition. Keep the product in water bath while Part B is being prepared.

16

Year 2

Organic Chemistry

Part B:
Couping reaction of the diazonium salt:
nitophenylazo)-2-naphthol (PARA Red)

Experiment 7
preparation of 1-(p-

Dissolve 1.44 g (0.01 mol) 2-naphthol in 25 mL 10% sodium hydroxide solution. Cool the
mixture to 10 oC and add slowly to the diazonium salts prepared earlier (in part A).
Acidify the mixture and collect the mixture (use suction filteration). Recrystallise the
product with either toluene or acetic acid and take the melting poing of the product.
Question:
1. Why do you have to keep the temperature at 10 oC when preparing the
diazonium salt?
2. Write the mechanism for the formation of the p-nitrobenzenediazonium sulfate.
3. What causes the colour observed in PARA Red?

17

Year 2

Organic Chemistry

Qualitative Analysis

QUALITATIVE ORGANIC ANALYSIS

The identification and characterization of an unknown organic compound normally refers
to those processes or tests that need to be performed in order to answer the following
important questions:
1.
What kind of functional groups are in the compound?
2.
Where in the molecule are these functional groups located?
3.
What is the position of one functional group in relation to another?
4.
Where a compound might exist as regio-, geometic or stereoisomers
(diastereomers or enantiomers), can the type of isomerism be specified?
It is usually good practice before these questions can be answered, to ask some
preliminary questions?
1a What kind of elements (carbon, hydrogen, nitrogen e.t.c) are in the compound?
2a What is the melting point or boiling point (if liquid) of the compound? This
question is of particular importance since if a library of compounds or a data base
of previously prepared compounds is available, agreement between the melting
point or spectroscopic data for your compound and the reference compound from
the published literature, can play a significant role in identifying an unknown
compound, provided it is pure. This leads naturally to the next point.
3a Purification of your compound by recrystallisation, chromatography or (if liquid) by
distillation is often essential.
Although it is possible, with modern spectroscopic equipment to completely identify a
compound, thereby providing complete structural information, it is strongly recommended
that you make use of other information for example, the physical state, elemental
analysis (point 1a above), solubility and confirmatory tests for functional groups.
Before we survey briefly the kind of tests you will need to perform, two important
points need to be emphasized, firstly, laboratories can be dangerous places for
the careless worker, therefore, make sure you protect your eyes by wearing safety
spectacles. This will be particularly important when you have to heat reaction
mixtures either to perform certain tests or during distillation. Wear a lab coat and
shoes that cover the feet. Secondly, be observant! Notice what is going on around
you in the laboratory for reasons of safety. Careful observation is also essential if
you are to obtain the maximum possible information from the chemical and
physical changes your compounds will undergo during the chemical tests.

Procedures
Preliminary observations
1. Check the purity of the sample. This can be done by either by TLC (thin layer
chromatography) or by GC (gas chromatography). If purification is necessary,
distillation or column chromatography will be required.
2. Note the colour. Colours may suggest to the experimenter the likely classification
of the compound. But this is not final proof, which, can only be obtained by
performing chemical tests and spectroscopic investigations. Common coloured
diketones (yellow), quinones (yellow to red), azo
compounds could include
compounds (yellow to red), and polyconjugated olefins and ketones (yellow to

18

Year 2

Organic Chemistry

Qualitative Analysis

red). It is not unusual to find that phenols and amines with colours ranging from
brown to dark purple because of traces of air oxidation products.
3. Note the odour. A fishy odour could suggest solid or liquid amines.The fragrance
of esters can be extremely pleasant. Alcohols, ketones, aromatic hydrocarbons,
and aliphatic olefins have characteristic odours. Thiols, isonitriles, and low
molecular weight carboxylic acids often have a rather unpleasant odour.
Caution: extreme care must be taken when the sense of smell is being used
in the laboratory, inhalation of unpleasant and perhaps toxic chemicals can
be dangerous.
4. For some investigations, you may be given a mixture of two compounds. In this
case you will need to perform tests for the presence of acidic or basic groups
followed by the appropriate extraction, where the compound is partitioned
between two solvents of different polarities in a separating funnel. The laboratory
assistant will teach you how to do this. Once this has been achieved, purification
(distillation or chromatography) can proceed.

Ignition test
Heating a small sample in a spatula in a Burnsen flame can be suggestive. If the
compound burns with a smoky flame it is probably an aromatic compound. If a large ashy
residue is left after is left after ignition, the unknown is probably a metal salt.
Elemental Analysis, The Sodium Fusion Experiment
In this test, the sample is added to hot sodium in a pyrex test tube. It is
important that you follow instructions, including the advice of your instructor,
faithfully and as always make sure you are wearing your safety glasses.
If nitrogen, sulphur or halogen are present in the unknown compound, these will be
converted to NaCN, Na2S and sodium halide (Cl, Br or I) respectively. These products
can in turn be readily identified. Of course caution is advisable when drawing inferences
from these observations. The presence of sulphur can interfere with the nitrogen test. In
addition, the sodium fusion test does not work well with nitro compounds.
Functional Group Tests
It is important to attempt to detect acidic or basic groups before you begin your functional
group tests. Adding a few drops of your unknown to a small volume of dilute hydrochloric
acid (2M) or dilute sodium hydroxide (2M), and careful observation to see if the sample
dissolves in the cold, will prove helpful.
Your reference book will provide you with information on a whole series of functional
group tests. For example, for aldehydes and ketones (addition of 2,4-dinitrophenyl
hydrazine resulting in the formation of a bright orange precipitate), for esters (addition of
KOH, HCl, FeCl3 resulting in the formation of the hydroxamic acid salt), for halogens ( the
silver nitrate test), for the nitro group (the purple colour produced by the titanous chloride
test). Tests for phenols, alcohols, primary and secondary amines, alkyl halides can be
obtained from the laboratory manuals. Further experiments for the formation and
purification of suitable derivatives for melting point determinations are also available.

19

Year 2

Organic Chemistry

Qualitative Analysis

References:
The Systematic Identification of Organic Compounds, Sixth edition,; Shriner, Fuson
Curtin and Morrill; Wiley,NY, 1980.
Kaedah Kimia dalam Pengenalpastian Sebatian Organik (Chemical Techniques for
Identification of Organic Compounds) (ISBN 983-100-069-2), Kamaliah Mahmood
dan Noorsaadah Abd. Rahman, Penerbit Universiti Malaya, 1998.
Kaedah Spektroskopi dalam Pengenalpastian Sebatian Organik (Spectroscopic
Techniques for Identification of Organic Compounds) (ISBN 983-100-018-8),
Kamaliah Mahmood dan Noorsaadah Abd. Rahman, Penerbit Universiti Malaya,
1997.
Introduction to Spectroscopy, Pavia, Lampman and Kriz; Saunders, NY, 1979.
Handbook of Tables for Organic Compound Identification" CRC Press.

20

Year 2

Organic Chemistry

Laboratory Notebooks

LABORATORY NOTEBOOKS
An entry in a laboratory notebook constitutes the primary reference to any experiment
one has personally carried out. It claims priority in any case of doubt.
All relevant aspects of a conversion should be recorded, together with the order in which
steps were carried out. All observations should be noted, in principle even those that at
first sight appear unimportant. Only in this way can one ensure that the results of critical
experiments can be reproducted.
At the beginning of each experiment record:

the date
structural formulae (abbreviated, if necessary) and all reagents in order of addition
molecular formulae and molecular weights, preferably under the relevant structural
formulae
literature references on the procedure (or on analogous preparations)
weights (and number of moles) of each compound used
list of apparatus (with sketches in unusual cases)
the purity of all compounds and solvents (which should have been determined!)
e.g. "Analar grade", "Freshly distilled from LiAlH4", "filtered through basic alumina,
Wolem, activity I", "single spot on t.l.c. (SiO2, hexane)", "pure by n.m.r.", etc.

During the course of the experiment keeping running notes

all observations (described exactly)


the order of individual operations and the time taken over each of them


all experiments used to keep a check on the course of the reaction
At the end of the reaction record without delay:


the method of working up


purification procedures


yields and percentage yields
Some hints:


Use a book with numbered pages


A book giving a carbon copy is a valuable safeguard!


Write your report on one side of the page only, using the facing page for recording
weights, distillation records, titrations, preliminary tests for separating mixtures,
hydrogenation curves, suggested improvements for future use, interpretation of
spectra, etc.


Note reference numbers of spectra in the margin (but keep the spectra themselves
in separate files).


An index makes it easier to retrieve the information.


For key experiments, write an edited report for later use and file it separately.


Some research workers also keep a diary to provide a very brief record of what
work they have done each day.

21

Year 2

Organic Chemistry

Laboratory Notebooks

WRITING A REPORT
A good clear report is easy to produce if one has a comprehensive description of the
work including all relevant data on the starting materials and products as well as all the
experimental details in one's laboratory notebook.
The experimental procedure should be described concisely with neat formulae and
relevant references.
A report on a preparative experiment should have the following features:

Title
This should include the name of the product, the names of the experiments, and, where
relevant, the date.
e.g.
"Isolation of cyclopenten-3-one from ......."
"Synthesis of cyclopenten-3-one from ......."

Report
This can be arranged in the following sections:
(a)

Method : Here the overall transformation carried out in each step of a multi-stage
synthesis is described.
e.g.
"Pinacol is prepared by the reductive dimerisation of acetone"
"Endo-bicyclo[2,2,1]hept-2-ene-5-carboxylic acid is formed by the
cycloaddition (Diels-Alder Reaction) of cyclopentadiene and acrylic acid".

(b)

Reaction scheme : This shows the transformation of starting materials to products

by means of formulae (configurational or conformational if necessary). Reaction
conditions (reagents, solvents, catalysts, temperature, etc.) are indicated in
abbreviated form above and below the arrows in the usual way. The molecular
formulae and molecular weights can be appended to the relevant structures. All
structures should be numbered. In general, diagrams showing mechanisms are
presented separately.

(c)

Experimental section : The description of the experiments (past tense, third

person, passive voice) should be sufficiently detailed to permit the repetition of the
reaction without further consultation of the literature. The report should be
sufficiently complete for it to be used in preparing a paper for publication. The
weights of all compounds (and the number of moles), the purity of starting
materials and solvents (these data on substances used repeatedly in a series of
experiments can be collected and placed at the beginning of the experimental
section, if desired), and all relevant reaction conditions (temperature, time,
pressure, etc.) should be quoted, as well as the work-up and purification
procedures. One should also provide information about the apparatus used, any
peculiarities observed, and simple procedures for the following the course of the
reaction.
In the text, names of all chemicals should be written out in full: formulae are used
only in reaction schemes. On the other hand, abbreviated or trivial names (with the

22

Year 2

Organic Chemistry

Laboratory Notebooks

structure numbers used in the reaction schemes) make it easier to follow

descriptions when long and complex names are involved.
The yield is quoted (not the average yield over several preparations) with an
indication of purity ("crude", "after recrystallisation", etc.), as well as the literature
yield with reference (where relevant).
Finally, the physical data used to characterise the compound should be reported
(again with literature references):
m.p., b.p., nD (with temperature superscript), Rf (with details of t.l.c. system, i.r.,
u.v., n.m.r., m.s., etc.

Some typical expressions and abbreviations

bright yellow crystals (10.5 mg, 78% based on 8)

tetramethylsuccinic anhydride (33.8 g, 0.217 mol)

nitrile (1.15 g, 8.5 mmol)

a solid residue (68.9 g) remained, and was recrystallised from ... (ca. 250 cm3) with
charcoal decolorisation

a absolute ethanol (2 cm3)

poured onto ice (1.5 kg)

in sodium hydroxide solution (1 N)

with methyllithium in ether (1.49 M, 16 cm3)

23

Year 2

Organic Chemistry

Laboratory Notebooks

Notebook Entry
16.5.1998
p. 45
O

H2N

Pb(OAc)4

H5 C6

C6H5

CH2Cl2

C6H5
O
C14H12

C8 H6N2O2

180

160

H5 C6

O
C22H16N2O2
340

Reference : L.A. Carpino and R.K. Kirkley, J. Am. Chem. Soc.,

92, 1784 (1970).
Apparatus : 300 cm 3-neck flask; mechanical stirrer with Teflon
blade
Reagents :

40 mmol
6.50 g (40 mmol) N-aminophthalamide
(m.p. 199.202). It solidifies after melting, perhaps
because of rearrangement to

O
NH
NH
O

36.0 g (0.2 mol 5-fold excess) trans-stilbene

(Fluka, "pursiss")
20.0 g (ca. 40 mmol) lead tetra-acetate
(Fluka, "purum", 85-90% moistened with
acetic acid).

N-aminophthalamide (4.50 g, 40 mmol) and trans-stilbene (36.0 g,

0.2 mol) were suspended in dichloromethane (100 cm3, distilled
over P2O5) and treated at room temperature and with vigorous
stirring over 10 min with lead tetra-acetate 20.0 g, ca 40 mmol),
added in portions. (The reaction mixture turned orange. Virtually
no heat was observed.
The mixture was stirred for a further 30 min, filtered through Celite
and evaporated (rotary evaporator, water bath at about 40 C).
The residue (a dark brown oil) was immediately chromatographed
on Kieselgel (190 g).
Dichloromethane eluted excess stilbene, a small amount of an
unidentified byproduct

p.46

24

Year 2

Organic Chemistry

Laboratory Notebooks

and a yellow crystalline compound (10.0 g, 73.5% calculated as 1phthalimido-trans-2,3-diphenylaziridine. The product was
recrystallised from chloroform-pentane.

Fraction 1

(Crystallisation overnight at 0, dried for 2 h at 0.05

torr/room temp.)
5.48 g (m.p. 177-179 C, lit.
(Carpino) m.p. 165 C)
tlc (Kieselgel)
Canary-yellow long needles
IR 43/1 (agrees with lit.!
Characterisation IR 43/1 (5% CHCl3)
NMR 43/1
MS 43/1 (200 C)
C-H-N microanalysis

Fraction 2 (ditto)
4.44 g (m.p. 176-177 C, tlc identical with Fraction 1)
IR 43/2 (identical with IR 43/1)
Yield :

IR 43/1
NMR 43/1
MS 43/1
microanalysis

IR 43/2

9.92 (73%)

Thermal stability: A sample was heated at

100 C for 15 h in an open fusion tube.
It showed no change (tlc, IR 43/3)

IR 43/3

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Year 2

Organic Chemistry

Laboratory Notebooks

EXAMPLE OF A LABORATORY REPORT

1-Phthalimido-trans-2,4-diphenylaxiridine

19 July 2006

(a)

Azhar Ariffin

Method
trans-Stilbene reacts with N-aminophthalimide in the presence of lead tetra-acetate
in antioxidatively induced (2 + 1) cycloaddition to yield 1-phthalimido-trans-2,3diphenylaziridine.1,2

(b)

Scheme
O

H2N

Pb(OAc)4

H5 C6

C6H5

CH2Cl2
C6H5
C14H12
mw : 180

(c)

O
C8H6N2O2
160

RT

H5 C6

O
C22H16N2O2
340

Experimental
N-Aminophthalimide3 (6.50 g, 40 mmol) and trans-stilbene4 (36.0 g, 200 mmol)
were vigorously stirred in dry dichloromethane4 (100 cm3) in a three-necked 500
cm3 flask fitted with a Teflon-bladed stirrer, a thermometer, and a powder funnel.
Lead tetraacetate6 (20.0 g, 40 mmol) was added at room temperature to the
suspension over 10 min. After a further 30 min stirring, the mixture was filtered
through Celite and concentrated on a rotary evaporator at 40 C. The crude

26

Year 2

Organic Chemistry

Laboratory Notebooks

product was at once transferred to a silica gel (190 g) column and the excess
stilbene eluted with dichloromethane. A second fraction containing a small amount
of an unidentified by-product was then eluted, followed by 1-phthalimido-trans-2,3diphenylazirdine (10 g).
The product was recrystallised overnight at 0 C from chloroform/pentane and the
yellow needles dried for 2 h at 25 C/0.05 torr. The yield of recrystallised material
m.p. 177-179 C was 5.48 g. A second crop of crystals (4.44 g), m.p. 176-177 C,
was obtained from the mother liquor.
Yield after chromatography : 10.0 g (73.5%)
Yield after crystallisation :
9.92 g (73.0%)
(d)

Physical data
Rf (t.l.c., silica gel, dichloromethane) : 0.44
m.p. 177-190 C (lit. 1m.p. 165 C)
vmax (chloroform): 1774 (m), 1718 (s) cm-1
(CDCl3, 60 MHZ): 3.96 and 4.97 (2H, ABq, J 6 Hz), 7.08-7.83 (14 H, m) ppm
m/z 340 (M+, 9%), 194 (100
Found: C, 77.55; H, 4.79; N, 8.29. Calculated for C22H16O2N2, C, 77.63; H, 4.74; N,
8.23%

(e)

Notes
If the filtrate obtained by filtration of the reaction mixture through Celite is treated
with at equal volume of pentane at 0 C, instead of being concentrated, a
crystalline precipitate is produced. Recrystallisation from pentane/dichloromethane
gives a yield of 55-65%.
Heating of the reaction mixture at 100 C for 15 h did not affect the result (i.r., t.l.c.).

(f)

References
1.
2.
3.
4.
5.
6.

L.A. Carpino and R.K. Kirkley, J. Am. Chem. Soc., 1970, 92, 1784.
D.J. Anderson, T.L. Gilchrist, D.C. Horwell and C.W. Rees, J. Chem. Soc.
(C), 1970, 576.
Fluka, pursiss.
Fluka, purum, m.p. 199-202
Distilled over phosphorus pentoxide
Fluka, purum, 85-90%, moistened with acetic acid.

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